JP2018532586A - Improved method for producing mercury adsorbent - Google Patents

Abstract

A method of preparing a mercury adsorbing material is realized. The method forms a copper / clay mixture by mixing dry clay and a dry copper source, forms a sulfur / clay mixture by mixing dry clay and a dry sulfur source, and forms a copper / clay mixture and sulfur / clay. Mixing the mixture to form a mercury adsorbent premix, and shearing the mercury adsorbent premix to form a mercury adsorbent material. Various substrates may be used with or in place of clay, and various additives may be added to copper, sulfur, clay or mixtures thereof. [Selection] Figure 2

Description

The present invention relates to a method for producing a composition used to remove mercury (organic mercury, Hg, Hg ⁺ and / or Hg ⁺² ) from a gas stream, such as natural gas, industrial chimneys, etc. Relates to a composition to be produced and to a method of using the composition to remove mercury (organic mercury, Hg, Hg ⁺ and / or Hg ⁺² ) from a gas stream, such as natural gas, industrial chimneys, etc. . The composition “mercury removal media” produced by the method is particularly useful for removing mercury from flue gas emitted by coal-fired power plants. The mercury (Hg) removal material is a homogeneous composition, preferably a homogeneous and sheared composition comprising layered phyllosilicate, sulfur and copper, resulting in a copper / sulfur / Includes a composition such that a clay material is obtained, and additives may be added during the manufacturing process of the mercury (Hg) removal material. The copper is ion-exchanged with clay cations (cations), and the sulfur reacts with the ion-exchanged free copper and, depending on the combination of each mechanism, a phyllosilicate bound copper sulfide phase. ) Is formed.

This application claims the benefit of US Provisional Application No. 62 / 249,009, filed Oct. 30, 2015, which is expressly incorporated herein by reference in its entirety, including any drawings. .

  Mercury emissions from coal-fired and oil-fired power plants have become a major environmental concern. Mercury (Hg) is a powerful neurotoxin that affects human health at very low concentrations. The largest mercury source in the United States is a coal-fired power plant. These coal-fired power plants account for one-third to one-half of total mercury emissions in the United States.

  Mercury emissions are mainly due to flue gas (exhaust gas) emitted from combustion coal. There are three basic forms of Hg in flue gas: elemental Hg, oxidized Hg and particle-bound mercury.

  Currently, the most common method for reducing mercury emissions from coal-fired and oil-fired power plants is to inject powdered activated carbon into the flue stream. The activated carbon forms a high surface area material for mercury adsorption and particle bound mercury (PBM) aggregation. The disadvantage of adding activated carbon in the flue stream is the retention of the activated carbon in the fly ash waste stream. Fly ash discharged from coal-fired power plants is often added to concrete that is adversely affected by the presence of activated carbon.

  Another way to reduce Hg release is by adding species that react with mercury to chemisorb elemental Hg and oxidized Hg. One class of materials that can chemically react with Hg are metal sulfides. U.S. Pat. No. 6,719,828 teaches the preparation of sorbents such as clays with metal sulfides between the clay layers. The method used to prepare the layered adsorbent is based on an ion exchange process that limits substrate options to only substrates with high ion exchange capacity. Furthermore, the disclosed ion exchange is time consuming and requires several wet process steps that significantly impair reproducibility, performance, scalability, equipment requirements, and adsorbent costs. The process for producing an adsorbent according to the teaching of US Pat. No. 6,721,828 involves swelling the clay in an acidified solution, introducing a metal salt solution to exchange metal ions between the clay layers, and the ion-exchanged clay. The clay is redispersed in solution, the clay is sulfided by adding a sulfide solution, and finally the material is filtered and dried. Another disadvantage of the process disclosed in US Pat. No. 6,721,828 is the environmental liability of the by-products of the ion exchange process, ie, metal ion effluents and hydrogen sulfide produced.

  Published U.S. Patent Application No. 11/291910 (U.S. Pat. No. 7,578,869, issued August 25, 2009) describes a metal sulfide / bentonite composite for removing mercury from a flue gas stream. Preparation is taught. The application teaches two methods for preparing the composite material, an initial wet process and a solid reactive grinding process. Both processes are similar in that the copper salt is mixed with bentonite clay and then the sulfide salt is added. These processes differ in the way in which the sulfide is added. In the first method, the sulfide salt is added by an “initial wet” procedure in which the sulfide salt is dissolved in water and added to the copper / clay mixture as an aqueous solution. In the second method, the sulfide salt is added through a “solid reactive grinding” process in which the sulfide salt hydrate is ground with the hydrated copper / clay mixture. According to another teaching in the application, the initial wetting method and solid grinding method are different from the “wet” method of US Pat. No. 6,719,828, because the copper ions are related to the cation ions of bentonite clay. This is because there is no ion exchange. The composite nature of the material produced in that application is determined by the powder X-ray diffraction spectrum that provides evidence of the formation of the same copper sulfide, Koberite (CuS), prepared in US Pat. No. 6,719,828. Supported.

  U.S. Patent Application No. 11/291091 (U.S. Pat. No. 7,578,869, issued August 25, 2009) is a very stable copper / ion exchange, copper salt and bentonite clay that is readily and easily ion-exchanged. The claim is abandoned (excluded) for the point at which the clay composition is produced. See, for example, the document Ding, Z. and R. L. Frost, "Thermal study of copper adsorption on montmorillonites", Thermochimica Acta, 2004, 416: 11-16. Analytical analysis of these compositions confirms both interlayer ion exchange (intercalation (insertion)) and copper salt edge adsorption. For example, the document El-Batouti et al. “Kinetics and thermodynamics studies of copper exchange on Na-montmorillonite clay mineral,” J. Colloid and Interface Sci., 2003, 259: 223-227.

  U.S. Pat. No. 8,268,744 describes a process for producing a mercury adsorbent. However, there is still a need to realize improved anti-fouling adsorbents and methods for their production. It would be desirable to provide an improved process for easily and inexpensively producing an adsorbent containing metal sulfide on a substrate.

US Pat. No. 6,721,828 US Pat. No. 7,578,869 US Pat. No. 8,268,744

Ding, Z. and R. L. Frost, "Thermal study of copper adsorption on montmorillonites" Thermochimica Acta, 2004, 416: 11-16 El-Batouti et al. "Kinetics and thermodynamics studies of copper exchange on Na-montmorillonite clay mineral," J. Colloid and Interface Sci., 2003, 259: 223-227

SUMMARY OF THE INVENTION A method for producing a mercury adsorbing material and the resulting mercury adsorbing material. The method involved producing a mercury adsorbing material from clay, copper source and sulfur source and optionally additives.

  A method for producing a mercury adsorbing material, and a produced mercury adsorbing material. A method for producing a mercury-adsorbing material comprises a dry clay having a moisture content of less than about 15% by weight and a moisture content consisting essentially of (as the main component) its hydrate (molecular water of hydration). A copper / clay mixture is prepared by admixing a dry copper source with and optionally additives; essentially (as the main component) dry clay having a moisture content of less than about 15% by weight A sulfur / clay mixture is prepared by mixing a dry sulfur source having a water content consisting only of the hydrated (molecular) molecular water and optionally an additive; the copper / clay mixture and the sulfur / Mixing the clay mixture with optional additives to form a pre-mixture of the mercury adsorbent, and shearing the mercury adsorbent pre-mixture to form the mercury adsorbent To do. In some embodiments, the mercury-adsorbing material produced by the method has an interlayer d (001) spacing of less than 12 mm when the mercury-adsorbing material contains less than about 4 wt% moisture, and the mercury-adsorbing material The powder X-ray diffraction pattern of the material is substantially free of a diffraction peak of 2.73 ± 0.01Å. In some embodiments, the ζ potential (zeta potential) of the mercury adsorbent material is greater than the ζ potential of the dried clay. In a preferred embodiment, shear is achieved by passing the mercury-adsorbing material through an extruder with a moisture content of about 15 wt% to about 40 wt%, more preferably about 20 wt% to about 30 wt%.

FIG. 1 is an exemplary process diagram for producing a mercury adsorbing material by shear mixing. FIG. 2 is a diagram of a montmorillonite structure showing d (001) plane spacing that can be measured by powder X-ray diffraction. FIG. 3 is a composite view of a powder X-ray diffraction pattern of sodium montmorillonite. The lines represent the low angle diffraction pattern of sodium montmorillonite containing about 0.9 wt.% To about 24.4 wt.% Moisture. FIG. 4 is a composite view of a powder X-ray diffraction pattern of the mercury adsorbing material described herein. The plurality of lines represents a low angle diffraction pattern of a material containing about 0.6 wt% to about 22 wt% moisture. FIG. 5 shows about 30 for each sample of sodium montmorillonite, sodium montmorillonite containing about 4.5 wt% covelite, and the mercury adsorbent material described herein containing 4.5 wt% copper sulfide. FIG. 5 is a composite diagram of 2θ powder X-ray diffraction patterns of 1 to 35 degrees.

  The phrase “as used herein” encompasses all of the specification, abstract, drawings (Figures), and claims.

  As used herein, unless otherwise expressly stated, use of the singular includes the plural and vice versa (use of the plural includes singular). That is, “a” and “the” refer to any one or more that the word modifies. For example, “a particle” may refer to one particle, two particles, and the like. Similarly, “the substrate material” may refer to one, two or more substrates (substrate materials). Similarly, terms such as “substrate materials” are not intended to be limiting, unless explicitly stated or otherwise obvious from the context, Substrate material) and a plurality of substrates.

  As used herein, unless otherwise specified, “about”, “essentially”, “substantially”, “substantially”, Any word representing an approximation such as and the like means that the element so modified need not be exactly as described, but can vary from the description. The extent to which the description can vary (range) depends on how large changes are set, and how large changes still have the characteristics, characteristics and capabilities of unmodified words or phrases As such, it depends on whether the modified form can be recognized by experts in this field. With the above considerations in mind, the numerical value modified by the approximate word here is ± 15% in some embodiments, ± 10% in some embodiments, and in some embodiments. ± 5% may vary from the stated value, or in some embodiments may be within a 95% reliable interval.

  As used herein, all numerical values representing physical values or measured values are subject to normal fluctuations (variations) and measurement errors.

  As used herein, any given range includes endpoints. For example, “a temperature between 10 ° C. and 30 ° C.” or “a temperature between 10 ° C. and 30 ° C.” includes 10 ° C. and 30 ° C. and any temperature between the two. Further, throughout this disclosure, various aspects of the invention can be presented in a range format. The description in range format is merely for convenience and brevity and should not be construed as an inflexible limitation on the scope of the invention. Accordingly, the description of a range should be considered to have specifically disclosed all the possible subranges and individual numerical values within that range. By way of example, descriptions of ranges such as 1 to 6 are subranges such as 1 to 3, 1 to 4, 1 to 5, 2 to 4, 2 to 6, 3 to 6, etc., and within that range Individual numbers, such as 1, 2, 3, 4, 5 and 6, should be considered as specifically disclosed. Unless explicitly stated or from a context explicitly limited to integers, a description of a range such as 1 to 6 is a subrange such as 1.5 to 5.5 and Individual non-integer values and ranges beginning or ending with non-integer values or ranges beginning with and ending with each non-integer value should be considered specifically disclosed. This applies regardless of the extent or width of the range.

  As used herein, a range may be expressed as “about” one particular value and / or “about” another particular value. When such a range is expressed, alternative embodiments from one particular value and / or to another particular value are included. Similarly, when each value is expressed as an approximation with a preceding “about”, it is understood that the particular value forms another embodiment. As a non-limiting example, when “about 1 to about 4” is disclosed, another embodiment is “1 to 4”, even if not explicitly disclosed. Similarly, if one disclosed embodiment is at a temperature of “about 30 ° C.”, another embodiment is “30 ° C.”, even if not explicitly disclosed.

  As used herein, the use of “preferred”, “preferably” or “more preferable” to modify embodiments of the present invention refers to preferences that existed at the time of filing a patent application. .

  As used herein, “optional” means that an element that is modified by the term may or may not be present.

  As used herein, the phrase “any combination of” followed by a list joined by the conjunction “and” (preceding in Japanese) means that each element of the group is the conjunction “and Means any combination of two or more elements of a group such that each element of the list is linked by. As a non-limiting example, “any combination of A, B, C and D” means each of the following combinations: A and B, A and C, A and D, B and C, B and D, C and D A, B, and C; A, B, and D; A, C, and D; B, C, and D; A, B, C, and D. Similarly, the phrase “X is A, B, C, D, or any combination thereof” means that X is A, X is B, X is C, X is D, Or X is “any combination of A, B, C and D”, where the definition of “any combination thereof” above applies.

  As used herein, the phrase “wt%” refers to weight percentage.

  As used herein, when referring to the composition of the mercury sorbent material product, the weight percent is the weight percent after the mercury sorbent material has been dried, 5 wt% moisture and / or solvent, or lower content. % By weight such that an amount of moisture and / or solvent is present.

Angstrom (ス ト ロ) is a unit of length equal to 10 ⁻¹⁰ m, or 1Å = 1 × 10 ⁻¹⁰ m.

1 micron (μ) is a unit of length equal to 10 ⁻⁶ m, or 1 micron = 1 μm = 1 × 10 ⁻⁶ m.

  As used herein, reference to screening with a particular mesh size screen refers to a standard US mesh size.

  As used herein, a “particle” is a mass of material held together by physical bonding of molecules, agglomeration of multiple mass materials held together by colloidal forces and / or surface forces. (Multiple "particles"), a mass of materials held together by chemical bonds, such as a crosslinked polymer network, a mass of materials formed by ionic interactions, or agglomeration, surface forces, colloidal forces, ionic interactions A mass of material held together by any combination of action and chemical bonds. For the purposes of this disclosure, particles are defined as having a size ranging from less than a tenth of a 1 nm (0.1 nm) to a few cm in size.

The polydispersity of a plurality of particles represents a distribution of sizes, usually expressed as particle diameters, within the plurality of particles. Average diameter (diameter) may be a diameter of the number-average, wherein the number-average diameter _{(number average diameter) = Σ i} d i n i / Σ i n i, where in _{n i} is _{d i} Represents the number of particles having the diameter represented. Usually, an approximation is made and the distribution of particles by diameter is represented as a histogram, or in other words, the particles are divided into a plurality of smaller groups containing a smaller range of diameters, and each county of these groups is A diameter near the center of each range is assigned. The surface area average diameter is determined by (Σ _i f _i d _i ² ) ^1/2 and the volume average diameter is (Σ _i f _i d _i ³ ) ^1/3 . Where f _i is n _i / Σ _i n _i . Table Accordingly, if the surface area mean diameter, is the weighting coefficient, the surface area represented by the class of the particle diameter d _i (class), when the volume average diameter, weighting factors for each class of the particle diameter d _i Is the volume to be played. Since the surface area increases with the square of the diameter and the volume increases with the cube of the diameter, the surface area average diameter is larger than the number average diameter, and the volume average diameter exceeds the surface area average diameter. The mass or weight average diameter is the same as the volume average diameter when all particles have the same density. Similarly, the particle size distribution may be based on the number, surface area or volume of the particles.

  Another means for determining the mean diameter is through the use of dynamic light scattering, also called photon correlation spectroscopy, which measures the diffusion of particles in solution. The average diameter is an average hydrodynamic diameter and is close to the volume average diameter. One method is outlined in the International Organization for Standardization (“ISO”) 13320.

  The distribution of particle sizes may be represented by standard deviation, a well-known statistical measurement. Standard deviation may be suitable for narrow particle size distributions. Other measures of polydispersity include d10, which refers to the diameter at which 10% of the distribution represents the threshold below it, and d90, which refers to the diameter at which 90% of the distribution represents the threshold below it. The average may be referred to as d50. Thus, in the case of number average, half or 50% of the number of particles has a diameter smaller than d50. In the case of volume average diameter, d50 represents a diameter such that half of the volume represented by the plurality is a particle having a diameter smaller than d50, or in other words, the cumulative volume of the plurality of particles as a function of diameter. Represents the intersection of 50% lines in the plot.

  As used herein, unless otherwise stated, references to average particle size refer to particle size measured by photon correlation spectroscopy close to the volume average particle size. Non-spherical particles are approximated as spheres.

  As used herein, unless otherwise stated, references to the average molecular weight of a polymer (or polymer) refer to the weight average molecular weight.

  An improvement in the process of US Pat. No. 8,268,744 is described herein and the product produced by the improved process is described. The method described in US Pat. No. 8,268,744 is described, and then the improvements are described here. An exemplary method is shown in FIG. 1, where the addition of sodium chloride is optional.

  Mercury adsorption (sorbent), a layered clay material containing copper and sulfur, produced by shearing adsorbent components (especially clay, copper source and sulfur source) using the improved method described herein ) A material is formed. The methods disclosed herein are accomplished by both ion exchange of clay cations with cations of the adsorbent copper component and disruption (interruption) of standard reaction pathways. Analytical analysis of the mercury-adsorbing material produced by the shear method described herein shows that the produced material does not contain the kinetic reaction products described in the prior art, and It is expected that the improved method described herein will produce a mercury adsorbing material with similar properties. In some embodiments, the method produces a diffraction peak that does not show a 2.73 ± 0.01 ± diffraction peak when a powder X-ray diffraction pattern of the mercury adsorbent is obtained, taking into account background noise. When a product or a powder X-ray diffraction pattern of a mercury adsorbent is obtained, the product is substantially free of a 2.73 ± 0.01７３ diffraction peak.

  According to one aspect (feature) of the method disclosed herein, the mercury adsorbing material produced by the method disclosed herein comprises a silicate clay material. The silicate clay (phyllosilicate) is smectite clay, such as bentonite, montmorillonite, hectorite, beidellite, saponite, Nontronite, volkonskoite, sauconite, and / or stevensite, and / or synthetic smectite derivative, especially fluorohectorite ) And laponite; mixed layered clays, especially rectonite and their synthetic derivatives; vermiculite, illite, micaceous minerals, and their synthetic derivatives ; Layered hydrated crystalline polysilicates, especially makatite, kanemite, octasilicate (illierite), magadiite And / or kenyaite; attapulgite, palygorskite, and / or sepoilite; or any combination thereof. The clay material should have exchangeable cations. The silicate clay material is preferably montmorillonite with exchangeable calcium and / or sodium ions. Multiple clay materials may be used in combination.

  Another important aspect of the method disclosed herein is the use of reactive copper compounds. As used herein, a reactive copper compound is a copper-containing material that reacts with sulfur and / or sulfide ions. The reactive copper compound provides (supply) a copper source to the methods and materials disclosed herein. The copper source is preferably a dry material. The dry copper source here is in the form of powder, flakes or crystals that do not contain any water (s) -of-hydration beyond the water structure within the crystal structure of the solid copper compound. Defined as a reactive copper compound. When used with respect to a copper source, “basically (as the main component) its hydrated (water) water content consisting solely of molecular water” means water whose water content can be determined by experts in the field. It means that it can be up to 10% by weight, up to 5% by weight or up to 3% by weight than the amount of water equivalent to (corresponding to) the sum molecular water. (As an example, when the water of hydration is 5 g per 95 g of the copper source, the water in the copper substance is (5 + 0.5) / (100 + 0.5) × 100% = 5.472% when the water content is 10% by weight. Non-limiting examples of copper compounds that form (supply) the copper source include copper acetate, copper acetylacetonate, copper bromide (Copper bromide), copper carbonate, copper chloride, copper chromate, copper ethylhexanoate, copper formate, copper gluconate , Copper hydroxide, copper iodide, copper molybdate, copper nitrate, copper oxide, copper perchlorate, pyrophosphoric acid Copper (copper pyrophosphate), copper selenide copper selenide, copper sulfate, copper telluride, copper tetrafluoroborate, copper thiocyanate, copper triflate, copper metal, copper alloys and The anhydrous and hydrated forms of the mixture are included. The copper source is preferably a Cu (II) salt having a copper cation and a copper salt anion (anion); more preferably, the copper source is a Cu (II) salt, where the copper salt anion and sodium Pairing with ions (pairing) is more enthalpy than pairing with copper cations; the copper source is even more preferably a Cu (II) salt, wherein the copper salt anion and calcium cation Pairing (pairing) is more enthalpy than pairing with a copper cation; even more preferably, the copper source is copper sulfate. A combination of multiple reactive copper compounds may be used.

Yet another important aspect of the process disclosed herein is the use of reactive sulfur compounds. As used herein, reactive sulfur compounds are sulfur-containing materials (materials) that react with copper and / or copper ions to form sulfur atoms or polysulfides. The reactive sulfur compound provides (supply) a sulfur source to the methods and materials disclosed herein. The sulfur source is preferably a dry material. A dry sulfur source is defined herein as a reactive sulfur compound in powdered, flake, crystalline or gaseous form that does not contain moisture beyond any hydrated water within the crystal structure of the solid sulfur source. The When used with respect to a sulfur source, “basically (as the main component) its hydrated (water) water content consisting solely of molecular water” means water whose water content can be determined by experts in the field. It means that it can be up to 10% by weight, up to 5% by weight or up to 3% by weight than the amount of water equivalent to (equivalent to) molecular water. (See example above). Non-limiting examples of sulfur compounds that form a sulfur source include sodium sulfide, sodium disulfide, sodium polysulfide, ammonium sulfide, ammonium disulfide, ammonium polysulfide, potassium sulfide, potassium disulfide, potassium polysulfide, The anhydrous and hydrated forms of calcium sulfide and mixtures thereof are included. Non-limiting examples of sulfur compounds that form a sulfur source include sulfur, hydrogen sulfide, hydrogen disulfide, aluminum sulfide, magnesium sulfide, thiolacetic acid, thiobenzoic acid and mixtures thereof. The anhydrous form is included. The sulfur source is preferably a sulfide or polysulfide salt, the sulfide source is more preferably a sulfide salt, the sulfide source is even more preferably sodium sulfide, and the sulfide source is Na ₂ Even more preferably, it is selected from S, Na ₂ S · 3H ₂ O and Na ₂ S · 9H ₂ O, and even more preferably the sulfide source is Na ₂ S · 3H ₂ O. A combination of multiple reactive sulfur compounds may be used.

  Yet another important aspect of the disclosed method is that there is no copper + sulfur chemistry prior to shearing of the reactive compound. One means for preventing the pre-shearing copper + sulfur reaction (nature) of the compound is by diluting the copper and sulfur sources with clay material. One skilled in the art will recognize that the reaction rate is concentration dependent and that the reaction of the copper and sulfide sources will be dependent as well (concentration). Furthermore, the reaction of the copper source and sulfide source is suppressed by the absence of free (free) water. The addition of water and the possible formation of copper and / or sulfide solutions will greatly improve the reaction rate between the copper and sulfide sources. Here, any solid reaction will depend on the mobility of the ions and the exposed surface area of the copper and sulfide sources, so this solid reaction is very slow (slow). Let's go.

  The copper source is preferably mixed with the clay material prior to adding the copper / clay mixture to the mechanical shearing device, as disclosed below. Similarly, the sulfur source is preferably mixed with the clay material prior to adding the sulfur / clay mixture to the mechanical shearing device. Optionally, prior to adding the mercury adsorbent pre-mixture to the mechanical shearing device, the copper / clay mixture and sulfur / clay mixture can be mixed to form a mercury adsorbent premix. Yet another method of feeding the material to the mechanical shearing device is to mix the clay material with a copper source and a sulfur source (optionally first adding the copper source to the clay material and then the sulfur source of the mercury adsorbent premix. Or any variation in order monomers). The expert will understand that the order of addition will vary depending on the particular (reactive compound) source. Alternatively, the copper / clay and sulfur / clay mixtures may be added independently (separately) to the mechanical shearing device. Adding single or multiple dry materials to the mechanical shearing device is possible by any means available to the expert in the field.

  In one embodiment, the copper / clay mixture and the sulfur / clay mixture are produced and mixed in a single process where the copper source and the sulfur source are added to the clay material. The mixture is then agitated and the copper and sulfur sources are distributed across the clay material with a non-shear mixer to form a mercury adsorbent premix. An example of a non-shear mixer is a paddle mixer.

Each mass of the added copper source (its copper source to its sulfide source) relative to the added sulfide source is adjusted to give the preferred molar ratios of copper ions to sulfide ions, the ratio of which is the copper atom And a measure of sulfur atoms. For example, when the sulfide source is polysulfide, the ratio of copper ion to sulfide ion represents the molar ratio of copper atom (ion) to sulfur atom, the latter (sulfur atom) having the chemical formula S _x ²⁻ . Where X is greater than 1. The ratio of copper ions to sulfide ions ranges from about 0.1 to about 10, from about 0.2 to about 5, or from about 0.3 to about 3. The ratio (Cu: S) is about 0.1, 0.2, 0.3, 0.4, 0.5, 0.7, 0.9, 1, 1.1, 1.2, 1. 3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, It is preferably 2.6, 2.7, 2.8, 2.9 or 3.0. When the sulfide source is polysulfide (polysulfide), the ratio is generally less than 1. In one preferred embodiment, the ratio of copper ions to sulfur ions is less than about 1, more preferably less than about 0.5, and in another preferred embodiment, the ratio is greater than about 1, more preferably Greater than about 2. In some embodiments, the ratio (Cu: S) ranges from 0.1 to 2.

  The copper source is added to the clay material in a weight ratio that approximately matches (matches) the cation exchange capacity of the clay. Cation exchange capacity is a measure of the molar equivalents of exchangeable clay cations, and its weight ratio is a measure of the molar equivalents of cation copper ions added to the clay. Preferably, about 10 to about 300 millimoles (mmol) of copper is added to about 100 g of clay, more preferably about 20 to about 200 mmol of Cu to about 100 g of clay. Even more preferably, about 50 to about 150 mmol of Cu is added to about 100 g of clay.

  Yet another important aspect of the method presented here is the shearing of the mercury adsorbent premix. As the mechanical shearing method, an extruder, an injection molding machine, a Banbury (registered trademark) type mixer, a Brabender (registered trademark) type mixer, a pin mixer, or the like may be used. Shearing is also achieved by introducing a copper / clay mixture and sulfur / clay mixture at one end of an extruder (uniaxial or biaxial screw) and receiving the sheared material at the other end of the extruder. be able to. The temperature of the material entering the extruder, the temperature of the extruder, the concentration of the material added to the extruder, the amount of water added to the extruder, the length of the extruder, the residence time of the material in the extruder, and the The design (single screw, twin screw, number of flights, channel depth, flight clearance, mixing zone, etc.) determines the amount of shear applied to the material. There are several variables to control.

  It is preferred that water be added to the mechanical shearing unit to facilitate (accelerate) shearing of the mercury adsorbent premix and the reaction of copper and clay (ion exchange) and the reaction of copper and sulfur. Due to variations in the design of most mechanical shear units, eg supply capacity, the amount of water added to the unit is defined by the weight percentage (% by weight) of water in the sheared material It is preferred that The mercury adsorbing material preferably contains from about 15 wt% to about 40 wt% moisture, more preferably from about 20 wt% to about 30 wt% moisture, even more preferably after leaving the mechanical shearing unit. Contains about 23 wt.% To about 28 wt.% Moisture.

  One method for determining the structure and composition of the materials disclosed herein is by powder X-ray diffraction (powder XRD). The powder XRD pattern of the clay material is characterized by a wide low (small) angle peak corresponding to the spacing between the silicate layers. Please refer to FIG. Often used to determine the water content (water content) of water-swellable clay is the angle, and the peak maximum of this low angle peak decreases with increasing layer spacing, FIG. Please refer. Here, the peak maximum value decreases as the amount of water adsorbed on the layer interval increases. For example, a 2θ diffraction angle of about 7 ° in sodium montmorillonite clay corresponds to an interlayer d (001) spacing of about 12 mm, and a 2θ angle of about 9 ° depends on the thickness of the clay platelet. Corresponding to a distance of the nearest d9 (001) plane of about 9 mm. Changes in the interlaminar d (001) plane spacing of the clay sample and montmorillonite clay with added copper ions were performed by “The Orientation and Interaction of Ethylenediamine Copper (II) with Montmorillonite” (Burba and McAtee) ( (Orientation and interaction of ethylenediamine copper (II) and montmorillonite), Clays and Clay Minerals, 1977, 25: 113-118. There, copper intercalation and multiplatelet bonding were reported, and the average interlaminar d (001) plane spacing of the Cu (II) montmorillonite sample was about 12.5 mm. The layered copper sulfide // silicate // copper sulfide material disclosed in US Pat. No. 6,721,828 is based on an interlayer d (001) significantly greater than 12.5 mm due to the additional thickness of the copper sulfide layer. Will have a face-to-face spacing. The copper sulfide material deposited (deposited) on the surface disclosed in U.S. Patent Application Publication No. 11/291910 (U.S. Pat. No. 7,578,869) has copper sulfide on the surface of the clay as taught therein. Will deposit the same interlayer d (001) spacing as the original montmorillonite (eg, FIG. 3). Here, it has been found that when the moisture content of the material is less than 4% by weight, the method and material have an interlayer d (001) spacing of less than about 12 mm. For example, see FIG. FIG. 4 shows that the materials and methods described herein are not compatible with the structure taught in the prior art.

Further, the mercury-adsorbing material produced by the method disclosed herein substantially comprises koberite, a copper sulfide mineral disclosed in US patent application Ser. No. 11/291910 (US Pat. No. 7,578,869). Not included. As used herein, the term “substantially free of kobelite” may refer to 1 wt% or less of kobelite, 0.5 wt% or less of kobelite, or 0.3 wt% or less of kobelite. Good. Coverite is a kinetic product of copper (II) ions and sulfide (S ²⁻ ) ions and has the chemical formula CuS. The Kobelite powder XRD pattern contains at least four characteristic (signature) reflections, three of which overlap with the reflections in the montmorillonite clay material. Reflection at 2.73 ± 0.01 mm (where the variation in reflection position depends in part on the accuracy of the diffractometer) is characteristic of the kobelite material and is observable in clay-dominated (dominant) samples It is. FIG. 5 shows three powder XRD patterns in the 2θ range of 30 ° to 35 °. The XRD pattern for clays without copper sulfide is shown at the bottom, the XRD pattern for clays containing 4.5 wt.% Kobelite is shown in the center and disclosed here containing 4.5 wt.% Equivalent copper sulfide. The XRD pattern of the finished clay material is shown at the top. The kobelite reflection at 2.73 mm was marked with a vertical dashed line. As clearly shown by the powder XRD pattern, the materials disclosed herein are substantially free of 2.73 ± 0.01７３ diffraction peaks. Here, “substantially free of a diffraction peak of 2.73 ± 0.01 mm” means a substance having 1% by weight of kobelite, 0.5% by weight of kobelite, or 0.3% by weight of kobelite. It may be a diffraction peak below the diffraction peak.

  Yet another important aspect of the method disclosed herein is that the zeta (ζ) potential value of the mercury sorbent material produced by the method disclosed herein is used to produce the mercury sorbent material. Higher than the ζ potential value of the clay material (less negative: less negative). Surface charge on microparticulates, such as clay, can often be determined by measuring zeta potential and / or electrophoretic mobility. Applicable clay structures here include Bragg et al., “Crystal Structures of Minerals”, pp. 166-382 (Cornell University Press 1965), which is partially composed of the silicon-oxygen (silicate) configuration described herein, which is incorporated herein for the structure and chemical formula of the silicate material. The silicate portion of the clay often has an anionic charge in equilibrium in the material by including alkali metal and / or alkaline earth cations. Suspensions of these substances and their zeta potential measurements form a means for assessing paring (cation pairing for silicates) in clay materials . The lower (more negative) the zeta potential, the greater the percentage or percentage (%) of weak ionic interaction between the cation and silicate. A higher (less negative) ζ potential indicates a stronger ionic or covalent interaction between the cation and the silicate. It will not be expected that the zeta potential of the clay material will change due to the mixing (blending) of the neutral and clay materials. Ion exchange of alkali metals and / or alkaline earth cations in clay materials changes the zeta potential when the exchanged ions have a different binding energy with (to) the silicate It will be expected.

  Yet another important aspect of the method disclosed herein is that the material produced by the method described herein is of a material size that can be captured by a coal-fired power plant particulate collector. That is. The average particle size is preferably greater than 0.1 μm, and even more preferably greater than 1 μm. The preferred average particle size of the mercury sorbent material described herein for sorption of mercury in the flue gas depends on the particulate collector at the individual power plant. Examples of particulate collectors include bag-house fabric filters, electrostatic precipitators, and cyclone dust collectors. As generally and well known in the art, larger particles are easier to remove from the flue gas. The majority (at least 50%) of the particles preferably have a diameter (particle size) in the range of about 1 to about 100 μm, more preferably in the range of about 1 to about 50 μm, most preferably about 10 to about 25 μm. Have a range of diameters.

  Unexpectedly, the shear process did not reduce the size (particle size) of the materials disclosed herein above. It is well known that shearing, particularly high shear mixing, reduces the particle size of the clay material by delamination of the silicate layer. Here, it has been found that the sheared material has a particle size that is larger than the particle size of the dried clay starting material (with a moisture content of less than about 15% by weight). It was also found that the particle size distribution changes based on the mechanical shearing method. Samples sheared with a pin mixer were found to have a majority average particle size of about 3.8 μm and a minority average particle size of about 20 μm. It was found that the sample sheared in the extruder had the same average particle size and an additional minor fraction average particle size of about 40 μm. Without being bound to any particular theory, the growth of 20 μm and 40 μm particle size materials can result in delamination of clay material, growth of copper sulfur material on the step edges, and charged copper sulfur phase. It is assumed that it is characteristic of agglomeration (agglomeration) of the exposed clay surface on or around it.

  Yet another important aspect of the method described herein is the irreversible binding of mercury from the flue gas stream to the mercury adsorbing material produced by the method described herein. Here, irreversible binding means that the sequestered or sequestered mercury does not leach out of the mercury adsorbing material by water or by a solvent that is primarily water (here “mainly water”). Means 75% by weight or more of water).

  In other embodiments of the methods described herein, other materials may be added to the materials used in the method described in US Pat. No. 8,268,744. Each additive to the process may be used individually or in combination. In one aspect of the method described herein, multiple alternatives to the clay material described in US Pat. No. 8,268,744 may be used. Multiple alternatives of clay material may be used individually or in combination. Additives to clay materials and substitutes for clay materials may be used in combination. These additives to the process, multiple alternatives to the clay material, and combinations thereof may improve processing or may improve the thermal stability of the resulting material. Or both the processing and the thermal stability of the produced material may be improved. Copper kobelite and excess sulfide are oxidized and, as mentioned above, copper can form kobelite in the presence of sulfur. Adding single or multiple drying materials to the mechanical shearing device can be done by any means available to those skilled in the art.

  In order to reduce oxidation during the manufacturing process, during storage (preservation), during use, or during combinations thereof, as an alternative to clay materials or to clay materials in the methods described herein A magnesium-based layered silicate may be used as an additive. Hectorite may be used as a clay material in place of or in addition to one or more of the clay materials described above. Talc, chloritic talc, chlorite clay, or any combination of talc, chlorite talc and chlorite clay is one or more of the above clay materials May be used instead of or in addition to. If hectorite, talc, chlorite talc, chlorite clay, or any combination thereof is used in addition to the (other) clay material, hectorite, talc, chlorite talc, chlorite clay, or any thereof The weight ratio of the combination of the (other) clay material is about 1:99 to about 99: 1, preferably about 1:19 to about 19: 1, more preferably about 1: 9 to about 9: 1. There may be. If hectorite, talc, chlorite talc, chlorite clay, or any combination thereof is used, it may be added separately to the mechanical shearing device, or it, if present, Before the pre-blend (pre-blend) is added to the mechanical shearing device, it may be added to or pre-blended to all or part of the (other) clay material. Alternatively, before being added to the mechanical shearing device, hectorite, talc, chlorite talc, chlorite clay, or any combination thereof may be added to the copper source, the sulfur source, or both the copper and sulfur sources, They may be added individually or in combination or pre-blended. Hectorite, talc, chlorite talc, chlorite clay, or any combination thereof may be added to the mechanical shearing device by any combination of the methods described above. Without being bound by any particular theory, the use of magnesium-based layered silicates (at room temperature) improves shelf stability (at room temperature) during storage or storage) It is assumed that

  Addition of inorganic dispersants and polymeric dispersants to materials used in the process as processing (processing) aids for clay dispersion, to reduce the covelite crystallinity, or combinations thereof As agents, they may be used individually or in combination. Non-limiting examples of dispersants include low, medium (and intermediate) and / or high weight average molecular weight tetrasodium pyrophosphate, sodium silicate (which has other performance features as well), poly Sodium acrylate and sodium polyaspartate are included. In the case of polyaspartate, the “low” weight average molecular weight Mw is less than 3000 g / mol, the “in” weight average molecular weight Mw is 3000 to 10,000 g / mol, and the “high” weight average molecular weight Mw is 10,000 g / mol. Greater than. Also, some types of dispersants, for example, without limitation, sodium silicate can serve other functions in addition to acting as a dispersant. The weight percentage of dispersant used is in the range of about 0.1% to about 10% by weight of the product produced, preferably in the range of about 1% to about 5% by weight of the product produced. There may be. The dispersant may be added separately to the mechanical shearing device, which (dispersant) is added individually or in combination or pre-blended to one or more other materials before being added to the mechanical shearing device. It may be dispersed, dissolved, or dispersed and dissolved in water, solvent, or a combination of water and solvent before being applied to the mechanical shearing device, or Any combination thereof may be used. The phrase “A may be blended individually or in combination with one or more materials” means that when the other materials are B and C, A is blended with B and an AB preblend (premix) A may be blended with C to form an AC preblend, A may be blended with B and C to form an ABC preblend, or some A May be blended with B to form an AB preblend, and some A may be blended with C to form an AC preblend, where B and / or C and May use all or part of material B and / or all or part of material C. Without being bound by any particular theory, the use of a dispersant to disperse the clay limits the agglomeration of the clay, thus disrupting (and hindering) and / or limiting the standard reaction pathway. It is assumed that the possible cation exchange is improved (enhanced). Without being bound by any particular theory, it is assumed that the use of a dispersant reduces the kobelite crystallinity by adsorbing to the surface of any formed kobelite and thus preventing the formation of a crystal lattice. Is done.

Without being bound to any particular theory, a pH stabilizer, oxygen scavenger (antioxidant), moisture scavenger (scavenger), or any combination thereof is used in the methods described herein. It is hypothesized that by adding to the material, the formation of copper sulfide / covelite oxide may be reduced during manufacturing, storage (preservation), use, or any combination thereof. Non-limiting examples of pH stabilizers that can be used individually or in combination as additives include sodium carbonate, sodium bicarbonate, lime (CaO), slaked lime, trona (trisodium bicarbonate dihydrate (trisodium Contains hydrogen-dicarbonate dihydrate, sodium sesquicarbonate or Na ₃ (CO ₃ ) (HCO ₃ ) · 2H ₂ O), calcium carbonate (calcite), and calcium magnesium carbonate (dolomite) . The weight percentage (%) of the pH stabilizer used is about 0.1% to about 50% by weight of the product produced, preferably about 1% to about 20% by weight of the product produced. Range, and in some embodiments it may range from 5% to 20% or from 10% to 20% by weight of the product produced. In some embodiments, the weight percentage of added pH stabilizer increases the pH of the material in the extruder, the pH of the material in the mixer, and / or the pH of the final product above the neutral pH (pH = 7). An amount sufficient to maintain, preferably in the range of about pH 9 to about 11, which is in the range of 0.1% to about 50% by weight of the product produced. Expected to get. In some embodiments, for example, without limitation, a substrate such as a silicate clay material incorporates one or more materials in the pH stabilizing materials described above, and in these embodiments, ( The weight percentage of added pH stabilizer (in addition to substances already present in the clay, substrate, or other materials not specifically added for pH effects) is about 0. 0% of the product produced. It may range from 1% to about 50%, preferably from about 1% to about 20% by weight of the product produced, and in some embodiments, 5% by weight of the product produced. It may be in the range of from 20% to 20% or from 10% to 20% by weight. The pH stabilizer may be added separately to the mechanical shearing device, which (pH stabilizer) is added or pre-blended to one or more other materials individually or in combination before being added to the mechanical shearing device. Or any combination thereof. In some embodiments, the pH stabilizer is added to the water added to the extruder, but this is not the preferred form of addition. In some embodiments, the pH stabilizer may be blended with the milled or sized particles after extrusion and drying, and / or, for example, prior to milling / sizing (after extrusion). ) May be blended with an intermediate. In some embodiments, about 0.001% to about 10% by weight of the final product is added to the milled / sized particles, or added to the intermediate (after extrusion), or the intermediate And (combined) pH stabilizers added to the milled / sized particles. In some embodiments, the substrate, such as a silicate clay material, includes one or more pH stabilizers, such as, without limitation, at least 3 wt%, at least 5 wt%, at least 7.5 wt%. % Or at least 10% by weight of one or more of the above-mentioned pH stabilizers are selected to be incorporated. In some embodiments, the combination described above is used to add a pH stabilizer.

  Non-limiting examples of oxygen scavengers (oxygen scavengers) that can be used individually or in combination as additives include sodium bisulfite and butylated hydroxytoluene, and radicals or oxygen Similar chemicals that can react with The weight percentage of oxygen scavenger used can range from about 0.001% to about 10% of the product produced, preferably from about 1% to about 3% by weight of the product produced. . The oxygen scavenger may be added separately to the mechanical shearing device, which (oxygen scavenger) may be added individually or in combination to one or more other materials before being added to the mechanical shearing device. Or it may be pre-blended and it will be dispersed, dissolved, or dispersed and dissolved in water, solvent, or a combination of water and solvent before being applied to the mechanical shearing device. It may be blended with the intermediate produced after drying and before milling, it may be blended with the product after milling, or any combination thereof.

  Non-limiting examples of moisture scavengers include calcium sulfate, calcium oxide, and calcium hydroxide. The weight percentage of moisture scavenger used is in the range of about 0.001% to about 15% by weight of the product produced, preferably about 0.5% to about 5% by weight of the product produced. It may be a range. The moisture scavenger may be added separately to the mechanical shearing device, which (water scavenger) may be added individually or in combination to one or more other materials added to the mechanical shearing device or pre-blended. It may be added or blended with the intermediate produced during the process after drying and before grinding, and it may be added or blended with the product after grinding. Or any combination thereof.

  In other embodiments of the methods described herein, other sulfur sources may be used individually or in combination in place of or in addition to those described above. Non-limiting examples of these other sulfur sources that may be used individually or in combination include elemental sulfur (elemental sulfur, elemental sulfur), sodium trithiocarbonate (sodium trithiocarbonate), thiol A silane having a functional group (or functionality) (a non-limiting example is gamma mercaptopropylmethoxy silane), sodium dimethyl-dithiocarbamate, and The sodium salt of trimercapto-s-triazine is included. The total (total) ratio of sulfur in the final product is adjusted so that the ratio of copper ions to sulfide ions is one of the above ranges or up to 20 wt% excess sulfur can be used. The In some embodiments, the weight ratio of other sulfur sources (as described in this paragraph) to standard sulfur sources (as described before this paragraph) was in the range of 1: 100 to 100: 1. Preferably, it is in the range of 1: 5 to 5: 1. If sulfur is used in addition to another sulfur source, it (sulfur) may be added separately to the mechanical shearing device, which is either individually or in combination before being added to the mechanical shearing device. More than one other material may be added or pre-blended (but preferably not a copper source in the absence of any other material), or any combination thereof. Without being bound by any particular theory, the formation of koberite during manufacturing, storage (storage), use, or any combination thereof is an alternative (optional) sulfur source. It is hypothesized that it can be made more complete and stable by substituting (adding) or adding sulfur from one of the.

In other embodiments of the methods described herein, higher surface area substrates may be utilized instead of or in addition to the clay materials described above. The higher surface area substrates may be used individually or in combination. Non-limiting examples of these higher surface area substrates include some of the above mentioned clay materials, including zeolite, attapulgite, sepiolite clay, imogolite clay, halloysite clay, perlite, vermiculite clay, fumed -Includes fumed silica, lignite, and bleaching earth clay. When one or more of the higher surface area substrates are used in addition to other clay materials, the weight ratio of the sum of those higher surface area substrates to the clay material is from about 1:99 to about 99: 1, preferably from about 1:19 to about 19: 1, more preferably from about 1: 9 to about 9: 1. The specific surface area of the clay material disclosed in US Pat. No. 8,268,744 determined by standard BET surface area analysis using nitrogen gas is in the range of about 1 to about 700 m ² / g, while higher surface area The specific surface area of the substrate is in the range of about 5 to about 1000 m ² / g. In some embodiments, the amount of higher surface area substrate added to the clay material is a ratio of the combination that is at least 20% higher, at least 30% higher, or at least 50% higher than the specific surface area of the clay material alone. Sufficient surface area is obtained. The higher surface area substrate may be added separately to the mechanical shearing device, or it (substrate), if present, before the preblend or combination is added to the mechanical shearing device. , Added to all or part of the clay material, or pre-blended. Alternatively, the higher surface area substrate may be added or pre-blended individually or in combination with the copper source, the sulfur source, or both the copper source and the sulfur source, prior to addition to the mechanical shearing device. . The higher surface area substrate may be added to the mechanical shearing device by any combination of the foregoing methods. Without being bound by any particular theory, it is assumed that the use of higher surface areas allows for more reaction sites and faster reaction times.

  In other aspects of the methods described herein, the higher surface area of the clay material may be obtained by an intercalation reagent that increases the spacing between silicates. FIG. 2 shows the spacing between the silicate layers. Intercalation reagents diffuse between the silicate layers and increase their spacing by increasing the distance between the silicate layers. Non-limiting examples of intercalation reagents that can be used individually or in combination include tetramethylammonium chloride, tetrabutylammonium chloride, trimethylcetylammonium chloride and tetraethoxysilane. The weight percentage of intercalation reagent used ranges from about 0.001% to about 15% by weight of the product produced, preferably from about 0.5% to about 5% by weight of the product produced. % Range may also be used. The intercalation reagent may be added separately to the mechanical shearing device, which (reagent) is added or preblended individually or in combination with one or more other materials added to the mechanical shearing device. Or it may be dispersed, dissolved, or dispersed and dissolved in water, solvent, or a combination of water and solvent before being applied to the mechanical shearing device, or A combination thereof may also be used. In a preferred embodiment, the intercalation reagent is added or blended into the clay before the clay / intercalation blend is added to the mechanical shearing device. Without being bound to any particular theory, the use of intercalation reagents provides access to more reactive sites (accessibility, accessibility) and faster diffusivity to those sites. Is assumed. In those embodiments where an intercalation reagent is used, the interlayer d (001) spacing may not be less than 12 mm when the mercury-adsorbing material produced by the method contains less than about 4% water by weight. is there.

  In those embodiments of the invention using or performing a blend or pre-blending, one component of the blend is much less than the other components of the blend (as a non-limiting example, 10 wt. Geometrical blends may be used (if less than 5% or less than 5% by weight).

  In other embodiments of the methods described herein, variations of the methods of US Pat. No. 8,268,744 described herein may be used in combination. As a non-limiting example, at least a portion of the clay material may be replaced with a higher surface area substrate, and more than one additive may be used during processing. Any combination of the above-described variations may be used.

  Also, embodiments of the present invention include products produced by the methods described herein, and products formed from phyllosilicates, sulfur sources, and copper sources, the additions described herein A product comprising at least one element in the group consisting of an agent, an alternative (optional) clay material as described herein, and an alternative sulfur source as described herein. In some embodiments of the present invention, it is a mercury adsorbent material comprising clay, copper source and sulfur source, and the powder X-ray diffraction pattern of the product substantially exhibits a peak of 2.73 ± 0.1Å. Not included.

Without being bound by any particular theory, the product of the process described herein, and / or an additive described herein, using an alternative clay material, an alternative source of sulfur The product formed by using or a combination thereof has the same or improved thermal stability compared to the product produced by the method described in US Pat. No. 8,268,744. The thermal stability of the product is measured by the color change. As described in the following examples, mercury adsorbent particles, such as those produced by the methods described herein, are pellets under appropriate pressure, such as, but not limited to, 200 psi (gauge) pressure. The resulting pellets are pressed into the shape of, for example, but not limited to, a LabScan XE (Label XE) device (manufactured by Hunter Associates Laboratory Inc.) It may be measured using a colorimeter. Each measurement is made immediately after manufacture (eg, without limitation, within 1 week, 48 hours, or 24 hours after manufacture), and each measurement is controlled in the laboratory at each sequential time. Measurements are made under different conditions. In some embodiments, a product produced by the methods described herein, and a product formed from a phyllosilicate, a sulfur source and a copper source, the additive described herein, A product comprising at least one element in the group consisting of the alternative clay material described herein and the alternative sulfur source described herein is a relative humidity (rh) at about 25 ° C. after 28 days. ) Can show a change in Hunter L or CIE L ^* value of 5 or less, 4 or less, 3 or less or 2 or less in the range of 20% to 50% (CIE: Commission Internationale de L'Eclairage) Meeting). In some embodiments, a product produced by the methods described herein, and a product formed from a phyllosilicate, a sulfur source and a copper source, the additive described herein, A product comprising at least one element in the group consisting of the alternative clay material described herein and the alternative sulfur source described herein is about 100 ° C. after 4 days (96 hours). Changes in the Hunter L value of 3 or less, 2.5 or less, 2 or less, or 1.5 or less may be exhibited in the range of 20% to 50% relative humidity (rh). In some embodiments, a product produced by the methods described herein, and a product formed from a phyllosilicate, a sulfur source and a copper source, the additive described herein, A product comprising at least one element in the group consisting of the alternative clay material described herein and the alternative sulfur source described herein is about 24Oh at about 160 ° C and a relative humidity (rh ) In the range of 20% to 50%, it may show a change in Hunter L value of 3 or less, 2.5 or less, 2 or less, or 1.5 or less.

  A mercury sorbent material obtained by the method described herein, and a mercury sorbent material formed from a phyllosilicate, a sulfur source and a copper source, the additive described herein, the alternative described herein A mercury adsorbent material comprising at least one element in the group consisting of a clay material and an alternative sulfur source described herein may be retained in a fly ash waste stream. While activated carbon containing fly ash can be detrimental to concrete formation and stability, it is preferred that mercury adsorbing materials containing fly ash are not detrimental to concrete formation and / or stability. Mercury adsorbent materials preferably do not increase the amount of air-entrainment agent (AEA) required for concrete formation, one measure (measured value) being the Foam Index test value. is there. More preferably, the mercury-adsorbing material does not adsorb or react with AEA, and the mercury-adsorbing material helps the AEA form stable 10-250 μm pockets in the final concrete. More preferably. Furthermore, it is preferred that the adsorbed (blocked) mercury does not leach out of the mercury sorbent material during or after the concrete formation process. Furthermore, it is preferable that deterioration of concrete is suppressed by including a mercury adsorbing material. Methods for inhibiting concrete degradation include limiting and / or preventing structural damage from alkali silicate reactions, carbonation, sulfuric acid attack, leaching, and / or freeze / thaw cycles. It is out. Without being bound by any particular theory, products produced by the methods described herein, and products formed from phyllosilicates, sulfur sources and copper sources, described herein The product comprising at least one element in the group consisting of the additive to be added, the alternative clay material described herein, and the alternative sulfur source described herein is water adsorption and expansion. It is preferred to suppress concrete degradation by limiting the amount, thereby improving the freeze / thaw cycle (circulation) of the concrete and / or inhibiting concrete degradation by preventing ion leaching. Another advantage of the materials described herein is the similarity of the bulk structure to cement, silicate-aluminate materials, preferably supporting the chemical bonding of the mercury adsorbing material to the prepared concrete. .

Mercury adsorbents can be tested and evaluated for performance under different conditions:

Laboratory bench scale testing uses nitrogen, air, or simulated flue gas, and typically the adsorbent is placed in a fixed bed. The simulated flue gas has a composition of SO ₂ , NO _x , HCl, CO ₂ , O ₂ , H ₂ O and HgO at high temperatures. The gas passes through the adsorbent bed at a certain flow rate (flow rate). The effluent gas is analyzed for its mercury concentration by a mercury analyzer. The test proceeds until adsorption equilibrium is reached. Both mercury removal efficiency and sorption capacity can be determined at the end of the test. Factors affecting the results are temperature, mercury oxidation state, and flue gas composition. Bench scale testing is a very economical method for screening adsorbents.

  Pilot (experimental) scale testing is very effective in studying adsorbent performance under conditions close to true industrial conditions. Test units are typically set up for in-flight testing. Simulated flue gas, or slip stream flue gas can be extracted from industrial facilities such as power plant ESP (electrostatic precipitator) or contain adsorbents A fibrous filter unit can be used to do this. Adsorbent is injected into the test system and the mercury concentration is monitored for changes in mercury concentration. The contact time between the adsorbent and the flue gas is only a few seconds.

  Finally, a full-scale power plant test can be prepared. The design and selection of the injection system and the rapid and accurate measurement of the mercury concentration are important factors (factors) during the evaluation period.

  Some non-limiting embodiments of the present invention are as follows.

Embodiment 1: The method for producing a mercury-adsorbing material is not limited,
Adding a mercury adsorbent component, or optionally a mercury adsorbent component, in the form of a mercury adsorbent premix, to a shearing device;
Here, the mercury adsorbent component is not limited,
A first dry clay, a second dry clay, or a combination of a first dry clay and a second dry clay;
A dry copper source,
A first dry sulfur source, a second dry sulfur source, or a combination of a first dry sulfur source and a second dry sulfur source;
Including
Further comprising forming the mercury adsorbent material by shearing the mercury adsorbent component using the shearing device,
At least one element (condition) of the group consisting of the following conditions (a), (b) and (c) is applied;
Condition (a) the mercury adsorbing material also includes an additive,
Condition (b) the presence of the second dry clay,
Condition (c) the presence of the second dry sulfur source;
The powder X-ray diffraction pattern of the mercury adsorbing material is substantially free of a diffraction peak of 2.73 ± 0.01Å.

Embodiment 2: In some embodiments, for example, without being limited to the method of Embodiment 1, the mercury adsorbent premix is formed,
Forming the mercury adsorbent premix is not limited,
By mixing dry clay and dry copper source, a copper / clay mixture is formed,
By mixing dry clay with a dry sulfur source, a sulfur / clay mixture is formed,
Mixing the copper / clay mixture and the sulfur / clay mixture to form the mercury adsorbent premix.

  Embodiment 3: In some embodiments, for example, without being limited to the method of Embodiment 1, the mercury adsorbent premix is formed, and forming the mercury adsorbent premix is limited. Without mixing the copper / clay mixture and the sulfur / clay mixture to form the mercury adsorbent premix.

  Embodiment 4: In some embodiments, for example and without limitation to the methods of Embodiments 1-3, the clay has a moisture content of less than about 15% by weight.

  Embodiment 5: In some embodiments, for example and without limitation to the methods of Embodiments 1-4, shearing is achieved by passing the mercury adsorbent component or premix through an extruder, the method Further includes adding water to the mercury adsorbent component or premix so that the extruded premix or extruded component has a moisture content of about 15 wt% to about 40 wt%.

  Embodiment 6: In some embodiments, for example and without limitation to the methods of Embodiments 1-4, shearing passes the mercury adsorbent component or premix through a pin mixer (pin mixer). The method further comprises adding the mercury adsorbent component or premix to the mercury adsorbent component or premix so that the premix or component contains about 15 wt% to about 40 wt% moisture when mixed in the pin mixer. Including adding water.

  Embodiment 7: In some embodiments, for example and without limitation to the methods of Embodiments 1-6, the mercury adsorbent includes a pH stabilizer.

  Embodiment 8: In some embodiments, for example and without limitation to the method of Embodiment 7, the pH stabilizer can be applied to one or more of the mercury adsorbent components, to the shearing device. Added to the mercury adsorbing material after shearing, optionally dried after shearing, to the mercury adsorbing material, or any combination thereof.

  Embodiment 9: In some embodiments, for example and without limitation to the methods of Embodiments 7 and 8, the pH stabilizer can be sodium carbonate, sodium bicarbonate, lime (CaO), slaked lime, trona (two Trisodium hydrogen-dicarbonate dihydrate, calcium carbonate (calcite), calcium magnesium carbonate (dolomite), or a combination thereof.

  Embodiment 10: In some embodiments, for example, without being limited to the methods of Embodiments 7-9, the produced mercury-adsorbing material has a moisture or solvent content of the material of 5% by weight or less. In some cases, 0.1 to 50% by weight of the pH stabilizer is included.

  Embodiment 11: In some embodiments, for example, without being limited to the methods of Embodiments 7-9, the produced mercury-adsorbing material has a moisture or solvent content of the material of 5% by weight or less. In some cases, 1 to 20% by weight of the pH stabilizer is included.

  Embodiment 12: In some embodiments, for example, without being limited to the methods of Embodiments 7-9, the produced mercury-adsorbing material has a moisture or solvent content of the material of 5% by weight or less. In some cases, 10 to 20% by weight of the pH stabilizer is included.

  Embodiment 13: In some embodiments, for example, without being limited to the methods of Embodiments 1-12, there is a first dry clay, and the first dry clay is not limited, Bentonite, montmorillonite, hectorite, beidellite, saponite, nontronite, volkonskoite, soconite, stevensite, fluorohectorite, laponite, lectonite, vermiculite, illite, mica mineral, A phyllosilicate selected from the group consisting of macatite, kanemite, octasilicate (Irielite), magadiaite, kenyanite, attapulgite, palygorskite, sepoilite, and any combination thereof.

  Embodiment 14: In some embodiments, for example and without limitation to the method of Embodiment 13, the first dry clay is present, and the first dry clay is not limited to montmorillonite. including.

  Embodiment 15: In some embodiments, for example, without limitation to the methods of Embodiments 1-14, the dry copper source is copper acetate, copper acetylacetonate, copper bromide, copper carbonate, copper chloride , Copper chromate, copper ethylhexanoate, copper formate, copper gluconate, copper hydroxide, copper iodide, copper molybdate, copper nitrate, copper oxide, copper perchlorate, copper pyrophosphate, copper selenide, copper sulfate A plurality of anhydrous copper compounds selected from the group consisting of copper telluride, copper tetrafluoroborate, copper thiocyanate, copper triflate, copper alloys, and mixtures thereof; and / or a hydrate of a certain copper compound Contains a copper salt selected from the group. Here, the copper compound of the hydrate is copper acetate, copper acetylacetonate, copper bromide, copper carbonate, copper chloride, copper chromate, copper ethylhexanoate, copper formate, copper gluconate, copper hydroxide, Copper iodide, copper molybdate, copper nitrate, copper oxide, copper perchlorate, copper pyrophosphate, copper selenide, copper sulfate, copper telluride, copper tetrafluoroborate, copper thiocyanate, copper triflate, copper alloys and One selected from the group consisting of the mixture.

  Embodiment 16: In some embodiments, for example, without limitation to Embodiments 1-15, there is a first dry sulfur source, and the first dry sulfur source is not limited, Sodium sulfide, sodium sulfide trihydrate, sodium sulfide nonahydrate, sodium disulfide, sodium polysulfide, ammonium sulfide, ammonium disulfide, ammonium polysulfide, potassium sulfide, disulfide Sulfur selected from the group consisting of potassium sulfide, potassium polysulfide, calcium polysulfide, hydrogen sulfide, hydrogen disulfide, aluminum sulfide, magnesium sulfide, thiolacetic acid, thiobenzoic acid, and mixtures thereof It is salt.

  Embodiment 17: In some embodiments, for example and without limitation to the methods of Embodiments 1-12, the first clay is present, the first clay is sodium bentonite, and the copper source Is copper sulfate pentahydrate, the first dry sulfur source is present, and the first dry sulfur source is sodium sulfide trihydrate.

  Embodiment 18: In some embodiments, for example, the second clay is present without being limited to the methods of Embodiments 1-17.

  Embodiment 19: In some embodiments, for example and without limitation to the method of Embodiment 18, the second clay is hectorite, talc, chlorite talc (chlorite talc). , Chlorite clay, zeolite, attapulgite, sepiolite clay, imogolite clay, halloysite clay, perlite, vermiculite clay, fumed silica, lignite, bleached clay, and combinations thereof.

  Embodiment 20: In some embodiments, for example and without limitation to the methods of Embodiments 18 and 19, the first dry clay source and the second dry clay source are present.

  Embodiment 21: In some embodiments, for example and without limitation to the method of Embodiment 20, the ratio of the weight of the second dry clay to the weight of the first dry clay is from 1:99 to The range is 99: 1.

  Embodiment 22: In some embodiments, for example, without being limited to the method of Embodiment 20, the ratio of the weight of the second dry clay to the weight of the first dry clay is from 1:19 to The range is 19: 1.

  Embodiment 23: In some embodiments, for example and without limitation to the method of Embodiment 20, the ratio of the weight of the second dry clay to the weight of the first dry clay is from 1: 9 to The range is 9: 1.

  Embodiment 24: In some embodiments, for example, without limitation to the methods of Embodiments 1-23, the second dry sulfur source is present.

  Embodiment 25: In some embodiments, for example and without limitation to the method of Embodiment 24, the second dry sulfur source has elemental sulfur, sodium trithiocarbonate, thiol functionality (functionality) It is selected from the group consisting of silane, sodium dimethyldithiocarbamate, sodium salt of trimercapto-s-triazine, and combinations thereof.

  Embodiment 26: In some embodiments, for example and without limitation to the methods of Embodiments 24 and 25, the first dry sulfur source and the second dry sulfur source are present.

  Embodiment 27: In some embodiments, for example and without limitation to the method of Embodiment 26, the produced mercury-adsorbing material is a mixture of the second dry sulfur source versus the first dry sulfur source. The weight ratio is in the range of 0.01: 1 to 1: 1.

  Embodiment 28: In some embodiments, for example and without limitation to the method of Embodiment 26, the produced mercury-adsorbing material is a mixture of the second dry sulfur source versus the second dry sulfur source. The weight ratio is in the range of 0.01: 1 to 1: 1.

  Embodiment 29: In some embodiments, for example, without being limited to the methods of Embodiments 1-28, a dispersion (sex) additive is present.

  Embodiment 30: In some embodiments, for example and without limitation to the method of Embodiment 29, the dispersion additive comprises tetrasodium pyrophosphate, sodium silicate, sodium polyacrylate, and low molecular weight (Mw <3000 g / mol) sodium polyaspartate, medium molecular weight (Mw = 3000 to 10,000 g / mol) polyaspartate, high medium molecular weight (Mw> 10000 g / mol) polyaspartate, and combinations thereof Selected.

  Embodiment 31: In some embodiments, for example, without being limited to the methods of Embodiments 29 and 30, the produced mercury adsorbent material has a moisture or solvent content of the material of 5% by weight or less. In some cases, the dispersion (sex) additive is included in an amount of 0.1 to 10% by weight.

  Embodiment 32: In some embodiments, for example and without limitation to the methods of Embodiments 29 and 30, the produced mercury-adsorbing material has a moisture or solvent content of the material of 5% by weight or less. In some cases, 1% to 5% by weight of the dispersing additive is included.

  Embodiment 33: In some embodiments, for example and without limitation to the methods of Embodiments 29-32, the dispersion additive can be added to one or more components of a plurality of mercury adsorbent components, as described above. Added to the shearing device to the mercury adsorbing material after shearing, optionally dried after shearing, to the mercury adsorbing material, or any combination thereof.

  Embodiment 34: In some embodiments, for example, without being limited to the methods of Embodiments 1-33, an oxygen scavenger (agent) additive is present.

  Embodiment 35: In some embodiments, for example and without limitation to the method of Embodiment 34, the oxygen scavenger (agent) additive is sodium bisulfite, butylated hydroxy Toluene, or a combination thereof.

  Embodiment 36: In some embodiments, for example and without limitation to the methods of Embodiments 34 and 35, the produced mercury-adsorbing material has a moisture or solvent content of the material of 5% by weight or less. In some cases, 0.001 wt% to 10 wt% of the oxygen scavenger is included.

  Embodiment 37: In some embodiments, for example and without limitation to the methods of Embodiments 34-36, the oxygen scavenger additive may be added to one or more of the components of the mercury adsorbent component. Added to the shearing device to the mercury adsorbing material after shearing, optionally dried after shearing, to the mercury adsorbing material, or any combination thereof.

  Embodiment 38: In some embodiments, for example, without being limited to the methods of Embodiments 1-37, a moisture scavenging (agent) additive is present.

  Embodiment 39: In some embodiments, for example and without limitation to the method of Embodiment 38, the moisture scavenging additive is calcium sulfate, calcium oxide, calcium hydroxide, or a combination thereof.

  Embodiment 40: For example, in some embodiments, without being limited to the methods of Embodiments 38 and 39, the produced mercury-adsorbing material has a moisture or solvent content of the material of 5% by weight or less. In some cases, 0.001% to 15% by weight of the moisture scavenging additive is included.

  Embodiment 41: In some embodiments, for example and without limitation to the methods of Embodiments 38 and 39, the produced mercury-adsorbing material has a moisture or solvent content of the material of 5% by weight or less. Some contain 0.5 wt% to 5 wt% moisture scavenging additive.

  Embodiment 42: In some embodiments, for example and without limitation to the methods of Embodiments 38-41, the moisture scavenging additive can be added to one or more of the components of the mercury adsorbent. Applied to a shearing device, to the mercury adsorbing material after shearing, optionally dried after shearing, to the mercury adsorbing material, or any combination thereof.

  Embodiment 43: In some embodiments, for example and without limitation to the methods of Embodiments 1-42, an intercalation reagent additive is present.

  Embodiment 44: In some embodiments, for example and without limitation to the method of Embodiment 43, the intercalation reagent additive may be tetramethylammonium chloride, tetrabutylammonium chloride, trimethylcetylammonium chloride, tetra Ethoxysilane, or a combination thereof.

  Embodiment 45: In some embodiments, for example and without limitation to the method of Embodiment 43, the produced mercury-adsorbing material has a moisture or solvent content of the material of 5% by weight or less. 0.001% to 15% by weight of the intercalation reagent additive.

  Embodiment 46: In some embodiments, for example and without limitation to the methods of Embodiments 43 and 44, the produced mercury-adsorbing material has a moisture or solvent content of the material of 5% by weight or less. In some cases, 0.5 to 5% by weight of the intercalation reagent additive is included.

  Embodiment 47: In some embodiments, for example and without limitation to the methods of Embodiments 43-46, the intercalation reagent additive is added to one or more components in the mercury adsorbent component. , To the shearing device, or any combination thereof.

Embodiment 48: The mercury adsorption material comprises a material,
The certain material is not limited,
A first clay, a second clay, or a combination of a first clay and a second clay;
A copper source,
A first sulfur source, a second sulfur source, or a combination of a first sulfur source and a second sulfur source;
Including
The next condition (a) is applied, the next condition (b) is applied, the next condition (c) is applied, or a combination thereof is applied,
Condition (a) the mercury adsorbing material also includes an additive,
Condition (b) the second clay is present,
Condition (c) the second sulfur source is present,
The mercury adsorbent material is substantially free of clay / covelite complex as determined by powder X-ray diffraction, and its powder X-ray diffraction pattern is substantially free of a peak of 2.73 ± 0.01Å. Is.

  Embodiment 49: In some embodiments, for example and without limitation to the mercury-adsorbing material of Embodiment 48, the molar ratio of copper to sulfur is less than 1.

  Embodiment 50: In some embodiments, for example and without limitation to the mercury-adsorbing material of Embodiment 49, the molar ratio is less than 0.5.

  Embodiment 51: In some embodiments, for example, without being limited to the mercury-adsorbing material of Embodiment 48, the molar ratio of copper to sulfur is greater than 1.

  Embodiment 52: In some embodiments, for example, without being limited to the mercury-adsorbing material of Embodiment 51, the ratio is greater than 2.

  Embodiment 53: In some embodiments, for example and without limitation to the mercury sorbent material of embodiments 48-52, the mercury sorbent material includes a pH stabilizer.

  Embodiment 54: In some embodiments, for example and without limitation to the mercury-adsorbing material of Embodiment 53, the pH stabilizer can be sodium carbonate, sodium bicarbonate, lime (CaO), slaked lime, trona (two Trisodium hydrogen carbonate dihydrate), calcium carbonate (calcite), calcium magnesium carbonate (dolomite), or combinations thereof.

  Embodiment 55: In some embodiments, for example, without being limited to the mercury sorbent material of Embodiments 53 and 54, the produced mercury sorbent material has a moisture or solvent content of the material of 5% by weight. When 0.1% to 50% by weight of the pH stabilizer is included.

  Embodiment 56: In some embodiments, for example and without limitation to the mercury sorbent materials of Embodiments 53 and 54, the produced mercury sorbent material has a moisture or solvent content of the material of 5 wt%. 1% to 20% by weight of the pH stabilizer is included when:

  Embodiment 57: In some embodiments, for example and without limitation to the mercury sorbent materials of Embodiments 53 and 54, the mercury sorbent material produced has a moisture or solvent content of the material of 5 wt%. 10% to 20% by weight of the pH stabilizer is included when:

  Embodiment 58: In some embodiments, for example, without limitation to the mercury-adsorbing materials of Embodiments 48-57, the first clay is present, and the first clay is bentonite, montmorillonite, hector Wright, beidellite, saponite, nontronite, volkonskoite, soconite, stevensite, fluorohectorite, laponite, lentite, vermiculite, illite, micaceous mineral, macatite , A phyllosilicate selected from the group consisting of: kanemite, octasilicate (Irielite), magadiite, kenyaite, attapulgite, palygorskite, sepolite, and combinations thereof.

  Embodiment 59: In some embodiments, for example and without limitation to the mercury adsorbing material of Embodiment 58, the first clay comprises montmorillonite.

  Embodiment 60: In some embodiments, for example and without limitation to the mercury-adsorbing materials of Embodiments 48-59, the dry copper source can be copper acetate, copper acetylacetonate, copper bromide, copper carbonate, Copper chloride, copper chromate, copper ethylhexanoate, copper formate, copper gluconate, copper hydroxide, copper iodide, copper molybdate, copper nitrate, copper oxide, copper perchlorate, copper pyrophosphate, copper selenide, A plurality of anhydrous copper compounds selected from the group consisting of copper sulfate, copper telluride, copper tetrafluoroborate, copper thiocyanate, copper triflate, copper alloys, and mixtures thereof; and / or one or more coppers A copper salt selected from the group consisting of compound hydrates. Here, the copper compound of the copper compound hydrate is copper acetate, copper acetylacetonate, copper bromide, copper carbonate, copper chloride, copper chromate, copper ethylhexanoate, copper formate, copper gluconate, hydroxide Copper, copper iodide, copper molybdate, copper nitrate, copper oxide, copper perchlorate, copper pyrophosphate, copper selenide, copper sulfate, copper telluride, copper tetrafluoroborate, copper thiocyanate, copper triflate, copper One selected from the group consisting of alloys and mixtures thereof.

  Embodiment 61: In some embodiments, for example, without being limited to the mercury-adsorbing materials of Embodiments 58-60, the first sulfur source is present, the first sulfur source is sodium sulfide, Sodium sulfide trihydrate, sodium sulfide nonahydrate, sodium disulfide, sodium polysulfide, ammonium sulfide, ammonium disulfide, ammonium polysulfide, potassium sulfide, potassium disulfide, potassium polysulfide, calcium polysulfide, hydrogen sulfide A sulfur salt selected from the group consisting of hydrogen disulfide, aluminum sulfide, magnesium sulfide, thiolacetic acid, thiobenzoic acid, and mixtures thereof.

  Embodiment 62: In some embodiments, for example, the second clay is present without being limited to the mercury-adsorbing materials of Embodiments 48-61.

  Embodiment 63: In some embodiments, for example and without limitation to the mercury adsorbing material of Embodiment 62, the second clay is hectorite, talc, chlorite talc, chlorite clay, zeolite, attapulgite , Sepiolite clay, imogolite clay, halloysite clay, perlite, vermiculite clay, fumed silica, lignite, bleached clay, and combinations thereof.

  Embodiment 64: In some embodiments, for example, without being limited to the mercury adsorbing materials of Embodiments 62 and 63, the first clay source and the second clay source are present.

  Embodiment 65: In some embodiments, for example and without limitation to the mercury adsorbing material of Embodiment 64, the ratio of the weight of the second clay to the weight of the first clay is from 1:99 to The range is 99: 1.

  Embodiment 66: In some embodiments, for example and without limitation to the mercury adsorbing material of Embodiment 64, the ratio of the weight of the second clay to the weight of the first clay is from 1:19 to The range is 19: 1.

  Embodiment 67: In some embodiments, for example and without limitation to the mercury adsorbing material of Embodiment 64, the ratio of the weight of the second clay to the weight of the first clay is from 1: 9 to The range is 9: 1.

  Embodiment 68: In some embodiments, for example, the second sulfur source is present without being limited to the mercury-adsorbing materials of Embodiments 48-67.

  Embodiment 69: In some embodiments, for example and without limitation to the mercury adsorbing material of Embodiment 68, the second sulfur source may be elemental sulfur, sodium trithiocarbonate, silane having a thiol functional group, dimethyl Selected from the group consisting of sodium dithiocarbamate, sodium salt of trimercapto-s-triazine, and combinations thereof.

  Embodiment 70: In some embodiments, for example and without limitation to the mercury adsorbing materials of Embodiments 68 and 69, the first sulfur source and the second sulfur source are present.

  Embodiment 71: In some embodiments, for example, without being limited to the mercury adsorbing material of embodiment 70, the produced mercury adsorbing material may be in the range of 0.01: 1 to 1: 1. A weight ratio of 2 sulfur sources to the first sulfur source.

  Embodiment 72: In some embodiments, for example and without limitation to the mercury adsorbing material of embodiment 70, the produced mercury adsorbing material may be in the range of 0.05: 1 to 1: 1. A weight ratio of 2 sulfur sources to the first sulfur source.

  Embodiment 73: In some embodiments, for example and without limitation to the mercury-adsorbing materials of Embodiments 48-72, a dispersing additive is present.

  Embodiment 74: In some embodiments, for example and without limitation to the mercury adsorbing material of Embodiment 73, the dispersion additive comprises tetrasodium pyrophosphate, sodium silicate, sodium polyacrylate, and low molecular weight (Mw <3000 g / mol) sodium polyaspartate, medium molecular weight (Mw = 3000 to 10,000 g / mol) polyaspartate, high medium molecular weight (Mw> 10000 g / mol) polyaspartate, and combinations thereof Selected from the group.

  Embodiment 75: In some embodiments, for example and without limitation to the mercury adsorbing materials of Embodiments 73 and 74, the produced mercury adsorbing material has a moisture or solvent content of the material of 5% by weight. In the following cases, the dispersion additive is contained in an amount of 0.1 to 10% by weight.

  Embodiment 76: In some embodiments, for example and without limitation to the mercury sorbent material of Embodiments 73 and 74, the produced mercury sorbent material has a moisture or solvent content of the material of 5% by weight. 1% to 5% by weight of the dispersion (sex) additive is included when

  Embodiment 78: In some embodiments, for example and without limitation to the mercury-adsorbing materials of Embodiments 48-72, a deoxygenating (agent) additive is present.

  Embodiment 79: In some embodiments, for example and without limitation to the mercury sorbent material of Embodiment 78, the deoxygenating additive is sodium bisulfite, butylated hydroxytoluene, or a combination thereof.

  Embodiment 80: In some embodiments, for example and without limitation to the mercury sorbent material of Embodiments 78 and 79, the produced mercury sorbent material has a moisture or solvent content of the material of 5% by weight. When present, it contains 0.001% to 10% by weight of the deoxygenating additive.

  Embodiment 81: In some embodiments, for example, without being limited to the mercury adsorbing materials of Embodiments 48-80, a moisture scavenging additive is present.

  Embodiment 82: In some embodiments, for example and without limitation to the mercury adsorbing material of Embodiment 81, the moisture scavenging additive is calcium sulfate, calcium oxide, calcium hydroxide, or a combination thereof.

  Embodiment 83: In some embodiments, for example and without limitation to the mercury sorbent material of Embodiments 81 and 82, the produced mercury sorbent material has a moisture or solvent content of the material of 5% by weight. When 0.005% to 15% by weight of the moisture scavenging additive is included.

  Embodiment 84: In some embodiments, for example and without limitation to the mercury sorbent materials of Embodiments 81 and 82, the produced mercury sorbent material has a moisture or solvent content of the material of 5% by weight. When containing 0.5% to 5% by weight of the moisture scavenging additive.

  Embodiment 85: In some embodiments, for example and without limitation to the mercury-adsorbing materials of Embodiments 48-84, an intercalation reagent additive is present.

  Embodiment 86: In some embodiments, for example and without limitation to the mercury adsorbing material of Embodiment 85, the intercalation reagent additive may be tetramethylammonium chloride, tetrabutylammonium chloride, trimethylcetylammonium chloride. , Tetraethoxysilane, or a combination thereof.

  Embodiment 87: In some embodiments, for example and without limitation to the mercury sorbent material of Embodiments 85 and 86, the produced mercury sorbent material has a moisture or solvent content of the material of 5% by weight. When 0.005% to 15% by weight of the intercalation reagent additive is included.

  Embodiment 88: In some embodiments, for example and without limitation to the mercury sorbent material of Embodiments 85 and 86, the produced mercury sorbent material has a moisture or solvent content of the material of 5% by weight. When 0.5% to 5% by weight of the intercalation reagent additive is included.

  Embodiment 89: In some embodiments, for example, without being limited to the mercury-adsorbing materials of Embodiments 48-88, the relative humidity (rh) 20% to 50 at about 25 ° C. (± 3 ° C.) after 28 days. The change in the Hunter L value of the mercury adsorbing material in the range of% is 5 or less.

  Embodiment 90: In some embodiments, for example, without being limited to the mercury-adsorbing materials of Embodiments 48-88, the relative humidity (rh) 20% to 50 at about 25 ° C. (± 3 ° C.) after 28 days. The change in Hunter L value of the mercury adsorbing material in the range of% is 4 or less.

  Embodiment 91: In some embodiments, for example, without being limited to the mercury-adsorbing materials of Embodiments 48-88, after about 28 days at about 25 ° C. (± 3 ° C.) relative humidity (rh) 20% to 50 The change in the Hunter L value of the mercury adsorbing material in the range of% is 3 or less.

  Embodiment 92: In some embodiments, for example, without being limited to the mercury-adsorbing materials of Embodiments 48-88, the relative humidity (rh) 20% to 50% at about 25 ° C. (± 3 ° C.) after 28 days. % Change in the Hunter L value of the mercury-adsorbing material is 2 or less.

Embodiment 93: In some embodiments, for example, without being limited to the mercury-adsorbing materials of Embodiments 48-88, after about 28 days at about 25 ° C. (± 3 ° C.) relative humidity (rh) 20% to 50 The change in CIE L ^* value of the mercury adsorbing material in the range of% is 5 or less.

Embodiment 94: In some embodiments, for example, without limitation to the mercury-adsorbing materials of Embodiments 48-88, after about 28 days at about 25 ° C. (± 3 ° C.) relative humidity (rh) 20% to 50 The change in CIE L ^* value of the mercury adsorbing material in the range of% is 4 or less.

Embodiment 95: In some embodiments, for example, without being limited to the mercury-adsorbing materials of Embodiments 48-88, after about 28 days at about 25 ° C. (± 3 ° C.) relative humidity (rh) 20% to 50 The change in CIE L ^* value of the mercury adsorbing material in the range of% is 3 or less.

Embodiment 96: In some embodiments, for example and without limitation to the mercury-adsorbing materials of Embodiments 48-88, after about 28 days at about 25 ° C. (± 3 ° C.) relative humidity (rh) 20% to 50 The change in CIE L ^* value of the mercury adsorbing material in the range of% is 2 or less.

  Embodiment 97: In some embodiments, for example and without limitation to the mercury-adsorbing materials of Embodiments 48-88, after about 96 hours at about 100 ° C. (± 5 ° C.) relative humidity (rh) 20% to 50 The change in the Hunter L value of the mercury adsorbing material in the range of% is 3 or less.

  Embodiment 98: In some embodiments, for example, without being limited to the mercury-adsorbing materials of Embodiments 48-88, relative humidity (rh) 20% to 50 at about 100 ° C. (± 5 ° C.) after 96 hours. The change in Hunter L value of the mercury adsorbing material in the range of% is 2.5 or less.

  Embodiment 99: In some embodiments, for example, without being limited to the mercury-adsorbing materials of Embodiments 48-88, relative humidity (rh) 20% to 50 at about 100 ° C. (± 5 ° C.) after 96 hours. % Change in the Hunter L value of the mercury-adsorbing material is 2 or less.

  Embodiment 100: In some embodiments, for example, without being limited to the mercury-adsorbing materials of Embodiments 48-88, relative humidity (rh) 20% to 50% at about 100 ° C. (± 5 ° C.) after 96 hours. % Change of the Hunter L value of the mercury adsorbing material in the range of 1.5% or less.

  Embodiment 101: In some embodiments, for example, without limitation to the mercury-adsorbing materials of Embodiments 48-88, after about 24 hours at about 160 ° C. (± 5 ° C.) relative humidity (rh) 20% to 50 The change in the Hunter L value of the mercury adsorbing material in the range of% is 3 or less.

  Embodiment 102: In some embodiments, for example, without limitation to the mercury-adsorbing materials of Embodiments 48-88, after about 24 hours at about 160 ° C. (± 5 ° C.) relative humidity (rh) 20% to 50 The change in Hunter L value of the mercury adsorbing material in the range of% is 2.5 or less.

  Embodiment 103: In some embodiments, for example, without limitation to the mercury-adsorbing materials of Embodiments 48-88, after about 24 hours at about 160 ° C. (± 5 ° C.) relative humidity (rh) 20% to 50 % Change in the Hunter L value of the mercury-adsorbing material is 2 or less.

  Embodiment 104: In some embodiments, for example, without being limited to the mercury-adsorbing materials of Embodiments 48-88, after about 24 hours at about 160 ° C. (± 5 ° C.) relative humidity (rh) 20% to 50 % Change of the Hunter L value of the mercury adsorbing material in the range of 1.5% or less.

Embodiment 105: A method of reducing oxidation in the manufacture of a mercury-adsorbing material, in storage, in use, or in any combination thereof, comprising:
The material contained in the mercury-adsorbing material contains clay, copper and sulfur, and substantially does not contain a clay / cobelite complex determined (measured) by powder X-ray diffraction. Substantially does not contain a peak of 73 ± 0.1Å
(A) adding a dispersant, oxygen scavenger, moisture scavenger, intercalation reagent, or any combination thereof;
(B) a second clay selected from the group consisting of talc, chlorite talc, chlorite clay, attapulgite, sepiolite clay, imogolite clay, halloysite clay, pearlite, lignite, bleached clay, and combinations thereof, wherein the clay Replacing or supplementing,
(C) a second sulfur source selected from the group consisting of elemental sulfur, sodium trithiocarbonate, silane having a thiol functional group, sodium dimethyldithiocarbamate, sodium salt of trimercapto-s-triazine, and combinations thereof, Replacing or supplementing the sulfur source,
Or any combination of (a), (b) and (c),
Including methods.

  In the above-described embodiments 1-105, the term “added to one or more of the mercury sorbent components” refers to the mercury adsorption. This includes adding the material to the premix if a premix is formed, as well as adding to any one or more of the ingredients.

Examples The following examples are given to illustrate the present invention, but are not intended to limit the scope of the invention.

Example 1-Comparative Example 368.5 g of sodium bentonite (85% passed through 325 mesh) in a kitchen aid stand mixer bowl (16%). 5 g of sodium chloride (from United Salt Corporation, passed through 20 mesh), 57.0 (g) of copper sulfate pentahydrate (Old Bridge Chemicals, Inc.) , 40 mesh), and 31.0 g of sodium sulfide trihydrate (Chem One Ltd.) were mixed for 5 minutes. 74.0 g of deionized water (pure water) was then added to the mixture and the mixture was stirred for 5 minutes. The mercury adsorbent mixture was then extruded (molded) three times using a laboratory scale extruder having a die plate. Subsequently, those extrudates (molded articles) were oven-dried at 100 ° C. The dried extrudate was ground and the resulting particles that passed through a 325 mesh screen were collected. The final moisture content of this sample was about 2% by weight.

Example 2-Comparative Example In a kitchen aid stand mixer bowl, 232.0 g sodium bentonite, 26.4 g sodium chloride, 91.2 g copper sulfate pentahydrate, and 49.6 g Of sodium sulfide trihydrate was mixed for 5 minutes. Then 52.4 g of deionized water (pure water) was added to the mixture and the mixture was stirred for 5 minutes. The mercury adsorbent mixture was then extruded (molded) three times using a laboratory scale extruder with a die plate. Subsequently, those extrudates (molded articles) were oven-dried at 70 ° C. The dried extrudate was ground and the resulting particles that passed through a 325 mesh screen were collected. The final moisture content of this sample was about 3.5% by weight.

Example 3-Comparative Example Mercury sorbent mixture was 2060 pounds (lbs) sodium bentonite, 92.2 pounds sodium chloride, 318.6 pounds copper sulfate pentahydrate, 173.3 pounds sodium sulfide trihydrate The material was prepared by mixing in a paddle mixer bowl. The mixture is mixed for 20 minutes, then a 5 inch READCO continuous processor (Readco Manufacturing Inc.) at a feed rate of about 900 pounds per hour (lb / hr). ). As the mercury adsorbent mixture is fed into the processor, water is fed into the processor through a liquid injection port (separated from the dry mixture feed port) at a flow rate of about 0.35 gallons / minute. It was. The extrudate was dried at about 100 ° C. and ground to reduce the particle size. The mercury adsorbing material has been found to have an average particle size of about 5 to about 25 μm and a moisture content of less than 10% by weight.

Example 4-Comparative Example Mercury sorbent mixture was 700 lbs sodium bentonite, 31.3 lbs sodium chloride, 108.3 lbs copper sulfate pentahydrate, 59.0 lbs sodium sulfide trihydrate. The material was prepared by mixing in a paddle mixer bowl. The mixture was mixed for 20 minutes and then fed to a 16 inch pin mixer (from Mars Mineral) at a feed rate of about 1100 pounds per hour (lb / hr). As the mercury adsorbent mixture is fed into the pin mixer, water enters the processor through a liquid injection port (separated from the dry mixture feed port) at a flow rate of about 0.35 gallons / minute. Supplied. The extrudate was dried at about 100 ° C. and ground to reduce particle size. The mercury adsorbing material has been found to have an average particle size of about 5 to about 25 μm and a moisture content of less than 10% by weight.

Example 5 (LH47 laboratory preparation process)
In a kitchen aid stand mixer bowl, 299.6 g sodium bentonite powder (approximately 50% through 325 mesh) and 14.0 g sodium chloride were mixed for 1 minute, then 47. 6 g of copper sulfate pentahydrate (manufactured by Chem One Ltd., Fine 30 grade) was added and mixed for another minute, and 38.8 g of sodium sulfide trihydrate (Chem One Ltd. .) Was added and mixed for 5 minutes. Then 57.2 g of deionized water (pure water) was added to the above dry mixture and mixed for an additional minute. The mercury adsorbent mixture was then extruded (molded) three times using a laboratory scale extruder with a die plate. The extrudates (molded articles) were then oven dried at 70 ° C. for about 18 hours. The dried extrudate was ground and the resulting particles that passed through a 325 mesh screen were collected. The final moisture content (rate) of this sample was less than 5% by weight.

Example 6 (LH57 laboratory preparation process)
240.0 g sodium bentonite powder (approx. 50% passed through 325 mesh) and 45.6 g Trona (Natronx Technologies, LLC) in a Kitchen Aid stand mixer bowl For 1 minute, then 64.0 g of copper sulfate pentahydrate (Chem One Ltd., Fine 30 grade) was added and mixed for an additional 1 minute to 50.4 g of sulfide. Sodium trihydrate (Chem One Ltd., flake form) was added and mixed for 5 minutes. 39.6 g of deionized water (pure water) was then added to the above dry mixture and mixed for an additional minute. The mercury adsorbent mixture was then extruded (molded) three times using a laboratory scale extruder with a die plate. The extrudates (molded articles) were then oven dried at 70 ° C. for about 18 hours. The dried extrudate was ground and the resulting particles passed through a 325 mesh screen and collected. The final moisture content of this sample was less than 5% by weight.

Example 7 (LH47 generation process)
At each hourly rate (hourly), 1872.5 pounds of sodium bentonite, 297.5 pounds of copper sulfate pentahydrate, 242.5 pounds of sodium sulfide trihydrate, and 87.5 pounds of sodium chloride Were simultaneously fed to a rotating continuous mixer (manufactured by Munson Machinery Company, Inc.) and mixed thoroughly or thoroughly. The resulting dry mixture is immediately about 2500 pounds into a 15 inch Extrud-O-Mix® extrusion processor (Bepex International LLC). / Hour supply rate. As the mercury adsorbent mixture was fed into the processor, water was fed into the processor through the liquid injection port at a flow rate of about 375 pounds / hour. The extrudate is dried using a fluid bed dryer (Carrier®) and further by a mill or pulverizer (Pulvocron, manufactured by Bepex International LLC). The particles were pulverized into fine particles having a particle size (particle size) distribution Dv50 (volume average particle size) of about 5 to 15 μm and a water content of less than 5% by weight.

Example 8 (LH57 generation process)
At each hourly rate (hourly), 1500 pounds of sodium bentonite, 400 pounds of copper sulfate pentahydrate, 315 pounds of sodium sulfide trihydrate and 285 pounds of trona are simultaneously rotating continuous mixer (Manson Machinery Company) (Munson Machinery Company, Inc.) and mixed thoroughly or thoroughly. The resulting dry mixture is immediately about 2500 pounds into a 15 inch Extrud-O-Mix® extrusion processor (Bepex International LLC). / Hour supply rate. As the mercury adsorbent mixture was fed into the processor, water was fed into the processor through the liquid injection port at a flow rate of about 250 pounds / hour. The extrudate is dried using a fluid bed dryer (Carrier®) and further by a mill or pulverizer (Pulvocron, manufactured by Bepex International LLC). The particles were pulverized into fine particles having a particle size (particle size) distribution Dv50 (volume average particle size) of about 5 to 15 μm and a water content of less than 5% by weight.

Example 9 (Sulfur additive with LH47, LH57 formulation, laboratory adjustment process)
240.0 g of sodium bentonite powder (about 50% through 325 mesh) and 20.0 g of elemental sulfur (Harwick Standard Distribution, Inc.) in a KitchenAid® stand mixer bowl Distribution Corporation grade 104) is mixed for 1 minute, 45.6 g of Trona (Natronx Technologies, LLC) is added and mixed for an additional minute, then 64.0 g of copper sulfate. Pentahydrate (Chem One Ltd., Fine 30 Grade) was added and mixed for an additional 1 minute, and 50.4 g of sodium sulfide trihydrate (Chem One Ltd., Flake form) was added and mixed for 5 minutes. 46.4 g of deionized water (pure water) was then added to the above dry mixture and mixed for an additional minute. The mercury adsorbent mixture was then extruded (molded) three times using a laboratory scale extruder with a die plate. The extrudates (molded articles) were then oven dried at 70 ° C. for about 18 hours. The dried extrudate was ground and the resulting particles passed through a 325 mesh screen and collected. The final moisture content of this sample was less than 5% by weight.

Example 10 (15NVEX3 manufacturing production process)
30000 pounds of sodium bentonite and 273 pounds of elemental sulfur (from InteGro, Inc.) were blended for 30 minutes using a ribbon blender to give a bentonite clay / sulfur preblend (premix). . At each hourly rate, 1500 pounds of sodium bentonite / sulfur pre-blend, 400 pounds of copper sulfate pentahydrate, 315 pounds of sodium sulfide trihydrate, and 285 pounds of trona are simultaneously rotating continuous mixer (Manson Supplied to Machinery Company (Munson Machinery Company, Inc.) and mixed thoroughly or thoroughly. The resulting dry mixture is immediately about 2500 pounds into a 15 inch Extrud-O-Mix® extrusion processor (Bepex International LLC). / Hour supply rate. As the mercury adsorbent mixture was fed into the processor, water was fed into the processor through the liquid injection port at a flow rate of about 250 pounds / hour. The extrudate is dried using a fluid bed dryer (Carrier®) and further by a mill or pulverizer (Pulvocron, manufactured by Bepex International LLC). The particles were pulverized into fine particles having a particle size (particle size) distribution Dv50 of about 5 to 15 μm and a water content of less than 5% by weight.

Test procedure for pH measurement 2.5 g of mercury adsorbent is dispersed in 47.5 g of deionized water using a 100 mL beaker and a magnetic stirrer with a mixing time of 5 minutes. . The pH of the resulting slurry is measured and reported using a laboratory pH meter.

Color Measurement Test Procedure Mercury adsorbent particles are pressed into pellets under a pressure of 200 psi. The resulting pellets are measured using a LabScan XE (Label XE) apparatus (manufactured by Hunter Associates Laboratory Inc). Unless otherwise indicated, CIE L ^* values are reported for black and white characteristics. Otherwise, the Hunter L value is reported for the same property.

Test Procedure for Mercury Adsorbent Stability at Ambient Conditions Mercury adsorbents were stored (stored) under laboratory conditions for extended periods of time at ambient temperature (18 ° C. to 23 ° C.). Samples (samples) were collected at the end of each time period and measured for chemical properties such as moisture content, pH and color.

Mercury sorbent oven stability test procedure The mercury sorbent is kept in the oven at a certain temperature (within about ± 2 ° C) for a long period of time, and at the end of a certain period a sample is collected, eg moisture Its chemical properties such as content, pH and color were measured.

Data for each formulation containing pH stabilizing reagent and its chemical stability improvement LH50, 51 as LH47 of Example 5, except that sodium chloride was replaced with sodium carbonate, sodium bicarbonate and quicklime, respectively. And 52 were prepared.

ＬＨ４７は本研究における比較参照試料であった。

LH47 was a comparative reference sample in this study.

LH39 was prepared as LH47, except that hectorite clay was used in place of sodium bentonite for each formulation containing magnesium-based layered silicate and improvement in its chemical stability .

ＬＨ４７は本研究における比較例（例７）であった。

LH47 was a comparative example (Example 7) in this study.

Data 15NVEX3 for each formulation containing elemental sulfur and sodium silicate was prepared as described in Example 10 and except that trona was replaced by sodium silicate (PQ Corporation, SS20 grade). 15NVEX4 was prepared as described in Example 8.

ＬＨ４７は本研究における比較参照試料であった。

LH47 was a comparative reference sample in this study.

Data on the combination of elemental sulfur and sodium silicate and its stability data 15NVEX8, except that the bentonite / sulfur preblend was of a different ratio and that the trona was replaced with a different ratio of sodium silicate Was prepared as in Example 10 and the detailed formulation is disclosed in Table 6. LH47 was a comparative reference sample in this study.

Data on Formulation with Higher Copper Sulfide Concentration and Its Impact on Stability Mercury sorbent with higher copper sulfide concentration in the same process as described in Example 7 using the formulation described in Table 8 .

ＬＨ４７は本研究における比較参照試料であった。

LH47 was a comparative reference sample in this study.

Data on formulations without copper sulfide No stability issues are expected with this type of formulation.

Example 11
Bentonite powder and sulfur powder (Harwick Standard Distribution Corporation, grade 104) were blended at a weight ratio of 93.3: 6.7, and the mixture was then fed at a feed rate of 900 pounds / hour. In a continuous processor manufactured by 5 inch Readco. Also, about 0.25 gal / min water and 1.04 gal / min quaternary ammonium chloride (aka “quat”) (AQUAD manufactured by Akzo Nobel) (Registered trademark)) 2HT, bis (hydrogenated tallow alkyl) dimethyl ammonium chloride (approximately 83% active), two independent of its Readco processor Supplied sequentially through the ports. The discharged extrudates from the processor are sent to a dryer where the dried extrudates are further crushed and have a moisture content of less than 5 wt. ) Granular particles were recovered as the final product.

  The above description is made for clarity of understanding only, and variations within the scope of the present invention may be apparent to those skilled in the art, so unnecessary limitations should not be understood from the description. Absent.

Claims (26)

A method for producing a mercury adsorbing material, comprising:
Adding a mercury adsorbent component, or optionally a premixed mercury adsorbent component, to a shearing device;
The mercury adsorbent component is
A first dry clay, a second dry clay, or a combination of a first dry clay and a second dry clay;
A dry copper source,
A first dry sulfur source, a second dry sulfur source, or a combination of a first dry sulfur source and a second dry sulfur source;
Including
At least one element of the group consisting of the following conditions (a), (b) and (c) is applied:
Condition (a) The mercury adsorbing material also includes an additive, and the additive is a dispersant, an oxygen scavenger, a moisture scavenger, an intercalation reagent, or any combination thereof,
Condition (b) The second dry clay is present, and the second dry clay is talc, chlorite talc, chlorite clay, attapulgite, sepiolite clay, imogolite clay, halloysite clay, perlite, lignite, bleached clay , And selected from the group consisting of combinations thereof,
Condition (c) The second dry sulfur source is present, and the second dry sulfur source includes elemental sulfur, sodium trithiocarbonate, silane having a thiol functional group, sodium dimethyldithiocarbamate, trimercapto-s-triazine. Being selected from the group consisting of sodium salts and combinations thereof;
Further comprising forming the mercury adsorbent material by shearing the mercury adsorbent component using the shearing device,
The powder X-ray diffraction pattern of the mercury adsorbing material is substantially free of a diffraction peak of 2.73 ± 0.01 mm.
Method. The mercury adsorbent component is made into the mercury adsorbent premix,
Producing the mercury adsorbent premix is:
Forming a copper / clay mixture by mixing dry clay and dry copper source;
Producing a sulfur / clay mixture by mixing dry clay and a dry sulfur source, and mixing the copper / clay mixture and the sulfur / clay mixture to form the mercury adsorbent premix;
Or a method according to claim 1, comprising any one of mixing a dry clay, a dry copper source and a dry sulfur source to form the mercury adsorbent premix.   The method of claim 2, wherein the dry clay has a moisture content of less than about 15% by weight. Shearing includes passing the mercury adsorbent component or premix through an extruder, the method further comprising from about 15% to about 40% by weight of the extruded mercury adsorbent component or premix. Adding water to the mercury adsorbent component or premix to have moisture,
Or shearing includes passing the mercury adsorbent component or premix through a pin mixer, and the method further includes: the mercury adsorbent component or premix when the mixture is mixed in the pin mixer. Adding water to the mercury adsorbent component or premix so as to have a water content of 15 wt% to about 40 wt%,
The method of claim 1.   The mercury adsorbing material includes a pH stabilizer, and the pH stabilizer is sodium carbonate, sodium bicarbonate, lime (CaO), slaked lime, trona (sodium bicarbonate dihydrate), calcium carbonate (calcite), The method of claim 1, which is calcium magnesium carbonate (dolomite), or a combination thereof.   The pH stabilizer may be applied to one or more mercury adsorbent components, to the shearing device, to the mercury adsorbing material after shearing, optionally dried after shearing, to the mercury adsorbing material, or any combination thereof. The method according to claim 5, which is to be added.   The produced mercury adsorption material includes 0.1 to 50 wt% of the pH stabilizer when the water or solvent content of the mercury adsorption material is 5 wt% or less. The method described.   The first dry clay is present, and the first dry clay is bentonite, montmorillonite, hectorite, beidellite, saponite, nontronite, forconscoite, soconite, stevensite, fluorohectorite, laponite, recto It contains a phyllosilicate selected from the group consisting of knight, vermiculite, illite, mica minerals, macatite, kanemite, octasilicate (Irielite), magadiite, kenyanite, attapulgite, palygorskite, sepoilite, and any combination thereof The method of claim 1. The dry copper source is copper acetate, copper acetylacetonate, copper bromide, copper carbonate, copper chloride, copper chromate, copper ethylhexanoate, copper formate, copper gluconate, copper hydroxide, copper iodide, molybdic acid The group consisting of copper, copper nitrate, copper oxide, copper perchlorate, copper pyrophosphate, copper selenide, copper sulfate, copper telluride, copper tetrafluoroborate, copper thiocyanate, copper triflate, copper alloys, and mixtures thereof A copper salt selected from the group consisting of a plurality of anhydrous copper compounds selected from: and / or certain copper compound hydrates;
Here, the copper compound of the copper compound hydrate is copper acetate, copper acetylacetonate, copper bromide, copper carbonate, copper chloride, copper chromate, copper ethylhexanoate, copper formate, copper gluconate, hydroxide Copper, copper iodide, copper molybdate, copper nitrate, copper oxide, copper perchlorate, copper pyrophosphate, copper selenide, copper sulfate, copper telluride, copper tetrafluoroborate, copper thiocyanate, copper triflate, copper 2. The method of claim 1, wherein the method is selected from the group consisting of alloys and mixtures thereof.   The first dry sulfur source is present, and the first dry sulfur source is sodium sulfide, sodium sulfide trihydrate, sodium sulfide nonahydrate, sodium disulfide, sodium polysulfide, ammonium sulfide, disulfide Selected from the group consisting of ammonium, ammonium polysulfide, potassium sulfide, potassium disulfide, potassium polysulfide, calcium polysulfide, hydrogen sulfide, hydrogen disulfide, aluminum sulfide, magnesium sulfide, thiolacetic acid, thiobenzoic acid, and mixtures thereof The process of claim 1, which is a sulfur salt. The first clay is present, the first clay is sodium bentonite;
The copper source is copper sulfate pentahydrate,
The first dry sulfur source is present and the first dry sulfur source is sodium sulfide trihydrate;
The method of claim 1. The second dry clay is present, or
The first dry clay and the second dry clay are present in a weight ratio of the second dry clay to the first dry clay ranging from 1:99 to 99: 1;
The method of claim 1. The second dry sulfur source is present, or
The first dry sulfur source and the second dry sulfur source are present in a weight ratio of the second dry sulfur source to the first dry sulfur source in the range of 0.01: 1 to 1: 1. ,
The method of claim 1.   After an additive is present, the additive is optionally dried after shearing, into the mercury adsorbent premix, into one or more mercury adsorbent components, into the shearing device, after shearing into the mercury adsorbent material, The method of claim 1, wherein the method is added to the mercury adsorbent material, or any combination thereof. The additive is selected from tetrasodium pyrophosphate, sodium silicate, sodium polyacrylate, low molecular weight sodium polyaspartate, medium molecular weight (Mw) polyaspartate, high medium molecular weight polyaspartate, and combinations thereof A dispersant,
The produced mercury adsorbing material contains 0.1 wt% to 10 wt% of the additive when the mercury adsorbing material has a water or solvent content of 5 wt% or less.
The method according to claim 14. The additive is present, the additive is an oxygen scavenger, and the additive is sodium bisulfite, butylated hydroxytoluene, or combinations thereof;
The generated mercury adsorbing material contains 0.001 wt% to 10 wt% of the additive when the moisture or solvent content of the material mercury adsorbing material is 5 wt% or less.
The method according to claim 14. The additive is a moisture scavenger, and the additive is calcium sulfate, calcium oxide, calcium hydroxide, or a combination thereof;
The produced mercury adsorbing material contains 0.001 wt% to 15 wt% of the additive when the mercury adsorbing material has a water or solvent content of 5 wt% or less.
The method according to claim 14. The additive is present, the additive is an intercalation reagent, and the additive is tetramethylammonium chloride, tetrabutylammonium chloride, trimethylcetylammonium chloride, tetraethoxysilane, or combinations thereof;
The produced mercury adsorbing material contains 0.001 wt% to 15 wt% of the additive when the mercury adsorbing material has a water or solvent content of 5 wt% or less.
The method of claim 1. A mercury adsorbing material containing a material,
The certain material is:
A first clay, a second clay, or a combination of a first clay and a second clay;
A dry copper source,
A first sulfur source, a second sulfur source, or a combination of a first sulfur source and a second sulfur source;
Including
At least one element of the group consisting of the following conditions (a), (b) and (c) is applied:
Condition (a) The mercury adsorbing material also includes an additive, and the additive is a dispersant, an oxygen scavenger, a moisture scavenger, an intercalation reagent, or any combination thereof,
Condition (b) The second clay is present and the second clay is talc, chlorite talc, chlorite clay, attapulgite, sepiolite clay, imogolite clay, halloysite clay, perlite, lignite, bleached clay, and Being selected from the group consisting of the combinations;
Condition (c) The second sulfur source is present, and the second sulfur source is elemental sulfur, sodium trithiocarbonate, silane having a thiol functional group, sodium dimethyldithiocarbamate, sodium salt of trimercapto-s-triazine. , And selected from the group consisting of combinations thereof,
The mercury adsorbing material is substantially free of clay / cobelite complex as determined by powder X-ray diffraction, and its powder X-ray diffraction pattern substantially contains a diffraction peak of 2.73 ± 0.01Å. Is not,
Mercury adsorption material. When the first clay is present, the first clay is bentonite, montmorillonite, hectorite, beidellite, saponite, nontronite, forconscoite, soconite, stevensite, fluorohectorite, laponite, lectonite. A phyllosilicate selected from the group consisting of: vermiculite, illite, mica minerals, macatite, kanemite, octasilicate (Irielite), magadiite, kenyanite, attapulgite, palygorskite, sepoilite, and mixtures thereof;
The dry copper source is copper acetate, copper acetylacetonate, copper bromide, copper carbonate, copper chloride, copper chromate, copper ethylhexanoate, copper formate, copper gluconate, copper hydroxide, copper iodide, molybdic acid The group consisting of copper, copper nitrate, copper oxide, copper perchlorate, copper pyrophosphate, copper selenide, copper sulfate, copper telluride, copper tetrafluoroborate, copper thiocyanate, copper triflate, copper alloys, and mixtures thereof A copper salt selected from the group consisting of: a plurality of anhydrous copper compounds selected from: and / or one or more certain copper compound hydrates;
The copper compound of the copper compound hydrate is copper acetate, copper acetylacetonate, copper bromide, copper carbonate, copper chloride, copper chromate, copper ethylhexanoate, copper formate, copper gluconate, copper hydroxide, iodine Copper fluoride, copper molybdate, copper nitrate, copper oxide, copper perchlorate, copper pyrophosphate, copper selenide, copper sulfate, copper telluride, copper tetrafluoroborate, copper thiocyanate, copper triflate, copper alloys and the like Is selected from the group consisting of mixtures,
When the first sulfur source is present, the first sulfur source is sodium sulfide, sodium sulfide trihydrate, sodium sulfide nonahydrate, sodium disulfide, sodium polysulfide, ammonium sulfide, ammonium disulfide. Elements in the group consisting of ammonium polysulfide, potassium sulfide, potassium disulfide, potassium polysulfide, calcium polysulfide, hydrogen sulfide, hydrogen disulfide, aluminum sulfide, magnesium sulfide, thiolacetic acid, thiobenzoic acid, and mixtures thereof Including
The mercury adsorption material according to claim 19.   The mercury adsorbing material contains a pH stabilizer, and the pH stabilizer is sodium carbonate, sodium bicarbonate, lime (CaO), slaked lime, trona (sodium bicarbonate dihydrate), calcium carbonate (calcite). The mercury adsorption material according to claim 20, which is calcium magnesium carbonate (dolomite), or a combination thereof. Additives are present,
The additive comprises the group consisting of tetrasodium pyrophosphate, sodium silicate, sodium polyacrylate, and low molecular weight sodium polyaspartate, medium molecular weight (Mw) polyaspartate, high and medium molecular weight polyaspartate, and combinations thereof Or the additive is an oxygen scavenger, the additive is sodium bisulfite, butylated hydroxytoluene, or a combination thereof, or the additive is a moisture scavenger The additive is calcium sulfate, calcium oxide, calcium hydroxide, or a combination thereof, or the additive is an iterating reagent, and the additive includes tetramethylammonium chloride, tetrabutylammonium chloride, chloride Trimethyl cetyl ammonium, tetraethoxy Run or a combination thereof, or any combination thereof,
20. A mercury sorbent material according to claim 19.   The mercury-adsorbing material according to claim 19, wherein the change in Hunter L value of the mercury-adsorbing material in a range of 20% to 50% relative humidity (rh) at about 25 ° C (± 3 ° C) after 28 days is 5 or less. . The mercury adsorption according to claim 19, wherein the change in CIE L ^* value of the mercury adsorbing material is about 5 or less in a range of 20% to 50% relative humidity (rh) at about 25 ° C (± 3 ° C) after 28 days. material.
The mercury adsorption material according to claim 19.   The mercury adsorbing material according to claim 19, wherein the change in the Hunter L value of the mercury adsorbing material in a range of 20% to 50% relative humidity (rh) at about 100 ° C (± 5 ° C) after 96 hours is 3 or less. .   The mercury adsorbing material according to claim 19, wherein the change in the Hunter L value of the mercury adsorbing material in a range of 20% to 50% relative humidity (rh) at about 160 ° C (± 5 ° C) after 24 hours is 3 or less. .

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